KR20060042924A - Hard laminate coating, process and apparatus for producing the same - Google Patents

Abstract

It is a hard laminated | multilayer film which alternately laminated | stacked layer A and layer B which consist of a specific composition so that the composition of layer A and layer B may differ. The thickness of layer A per layer is twice or more the thickness of layer B per layer, the thickness of layer B per layer is 0.5 nm or more, and the thickness of layer A per layer is 200 nm or less. The composition of layer A and layer B is a layer A having a cubic rock salt structure in which Ti, Cr, Al, V nitrides, carbonitrides, carbides, etc. are exemplified, and BN, BCN, SiN, SiC, SiCN, BC, Cu, It is set as the hard coat layer B which has crystal structures other than the cubic rock salt type structure which CuN, CuCN, metal Cu, etc. are illustrated. Or a layer A made of a chemical composition satisfying the following formula (8) and a layer B made of a chemical composition satisfying the following formula (9).

Formula 8

Layer A: Cr (B _a C _b N _1-abc O _c ) _e

0≤ a≤ 0.15, 0≤ b≤ 0.3, 0≤ c≤ 0.1, 0.2≤ e≤ 1.1

Formula 9

Layer B: B _1-st C _s N _t

0≤ s ≤0.25, (1-s-t) / t≤ 1.5

Or layer A consists of a specific atomic ratio composition of (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ), and layer B is B _1-xy C _x N _y , Si _{1- xy} C _x N _y , C _1-x N _x , Cu _1-y (C _x N _1-x ) _{y to} have a specific atomic ratio composition selected from the composition. Alternatively, the layer A is made of any one of the following Formula 1 or 6, layer B is to be made of the composition of the following formula (7).

Formula 1

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

Formula 6

(Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e

(X is a metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, Si)

Formula 7

M (B _a C _b N _1-abc O _c )

(M is a metal element selected from any one or more of W, Mo, V, and Nb)

Description

Hard Lamination Film, Manufacturing Method and Forming Apparatus {HARD LAMINATE COATING, PROCESS AND APPARATUS FOR PRODUCING THE SAME}             

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the laminated structure of the hard film of this invention.

2 is a cross-sectional view schematically showing a conventional hard film.

It is explanatory drawing which shows one aspect of the apparatus which forms a hard film of this invention.

It is explanatory drawing which shows another aspect of the apparatus which forms a hard film of this invention.

It is explanatory drawing which shows another aspect of the apparatus which forms a hard film of this invention.

It is explanatory drawing which shows the other aspect of the apparatus which forms a hard film of this invention.

It is a figure which shows the micro structure of the thickness direction cross section of the hard film which concerns on this invention. FIG. 7A is a schematic diagram, FIG. 7B is a longitudinal cross-sectional view.

8 is a front view showing another embodiment of the composite film forming apparatus of the present invention.

9 is a plan view showing another embodiment of the composite film deposition apparatus of the present invention.

It is explanatory drawing which shows the relationship between nitrogen partial pressure and nitrogen content in a hard film.

It is explanatory drawing which shows the relationship between nitrogen partial pressure and the surface roughness Ra of a hard film.

It is explanatory drawing which shows the relationship between the nitrogen partial pressure and the Vickers hardness of a hard film, respectively.

Fig. 13 shows one aspect of the sputtering evaporation source of the present invention, Fig. 13A is a plan view of the sputtering target material, and Fig. 13B is a front view of the sputtering evaporation source.

14 shows another embodiment of the sputtering evaporation source of the present invention, FIG. 14A is a plan view of the sputtering target material, and FIG. 14B is a front view of the sputtering evaporation source.

15 shows another embodiment of the sputtering evaporation source of the present invention, FIG. 15A is a plan view of the sputtering target material, and FIG. 15B is a front view of the sputtering evaporation source.

The present invention provides a hard laminated film having fine control of the crystal grain diameter to obtain excellent mechanical properties, a hard laminated film having abrasion resistance formed on a surface of a cutting tool or an automobile sliding member, and abrasion resistance and oxidation resistance. It is related with this excellent hard laminated film.

Moreover, this invention relates to the composite film-forming apparatus which is equipped with the arc evaporation source and the sputtering evaporation source, respectively, and can form the hard laminated film of the outstanding characteristic.

In recent years, the necessity of improvement of abrasion resistance of cutting tools based on cemented carbide, cermet, high-speed coated steel, etc., and sliding parts for automobiles is increasing, and the improvement of the wear-resistant coating used on the surface of these members is examined.

As this abrasion resistant film, conventionally, a hard film such as TiN, TiCN, TiAlN, which is a composite nitride film of Ti and Al, is coated on the base material (member shape).

In order to improve the wear resistance of these wear resistant films, attempts have been made to refine the crystal grains of the film by improving the properties mainly by adding a third element. For example, in the case of a cutting tool, it is reported that the oxidation resistance is improved by adding Si or B to the TiAlN film and at the same time, the hardness is increased by miniaturization of crystal grains (see US Patent No. 5,580,653 and US Patent No. 5,318,840). ). In addition, a method of improving the wear resistance by adding B to the CrN film used for the sliding member as a representative of the piston ring of an automobile is made high (see US Patent No. 6,232,003).

In addition, for the purpose of improving the characteristics by adding elements to the conventional hard film, while forming TiN as an arc evaporation source with an apparatus having an arc and a sputtering evaporation source, Si is added by sputtering to increase the hardness by forming a TiSiN film. Some attempts have been made to improve such properties (see KH Kim et al. Surf. Coat. Technol, 298 (2002) 243-244, 247).

In the method of refining the crystal grains of the film by adding an element to such a wear-resistant film, the degree of crystal grain refinement is determined according to the amount of the element added, and the particle diameter of the film can be controlled only by changing the amount. Therefore, in order to manufacture the film of a different particle diameter, it is necessary to produce many targets which changed the addition amount of an element. For this reason, making the sample of the particle diameter according to the objective, ie, the film which has the characteristic according to the objective, becomes very complicated, and there exists a practical problem.

In addition, as a hard film for cutting tools having excellent wear resistance even at high hardness, a hard film having a crystal structure mainly composed of a rock salt structure type has been proposed (US Patent No. 6,767,658, US Patent Publication No. 2002-168552). Reference). These hard film compositions are, for example, (Tia, Alb, Vc) (C1-d Nd), where 0.02≤a≤0.3, 0.5 <b≤0.8, 0.05 <c, 0.7≤b + c, a + b + c = 1, 0.5≤d ≤ 1 (a, b, c each represent an atomic ratio of Ti, Al, V, and d represents an atomic ratio of N) and the like.

In general, the hard film of the rock salt structure type can be measured by X-ray diffraction by the θ-2θ method. For example, a hard film such as (TiAlV) (CN) has a rock salt structure crystal structure, and constitutes a complex rock nitride salt compound in which Al and V are substituted at the Ti site of TiN of the rock salt structure type. In this case, AlN (lattice constant 4.12A) of the rock salt structure type is a high-temperature, high-pressure phase, and because it is a high hardness material, if the ratio of Al in (TiAlV) (CN) is increased while maintaining the rock salt structure, the hardness of the (TiAlV) (CN) film is Can be further increased.

As described above, there are apparatuses and methods for forming each hard film layer on a substrate by combining a plurality of arc evaporation sources, sputtering evaporation sources, or electron beam evaporation sources, respectively, depending on the hard material.

Among them, a device in which a plurality of arc evaporation sources or sputtering evaporation sources are combined to form a hard coating layer on the substrate, respectively, or sequentially, has a good film forming efficiency in that the film can be formed by utilizing different characteristics of the arc evaporation source and the sputtering evaporation source. It can be called a device.

For example, in comparing the characteristics of the arc evaporation source and the sputtering evaporation source, the arc evaporation is faster than the sputter evaporation, but it is difficult to adjust the film formation rate, and it is difficult to accurately control the thickness of the film layer of the thin film. On the other hand, the sputtering evaporation source is slower than the arc evaporation source, but it is easy to adjust the deposition rate and operates with a very small input power, so that the thickness of the film layer of the thin film can be precisely controlled.

For this reason, when an arc evaporation source is used for a relatively thick film layer and a sputtering evaporation source is used for a relatively thin film layer, thickness control of each film layer becomes easy, and a comprehensive film-forming speed can also be made quick.

BACKGROUND ART As a complex film forming apparatus in which a plurality of such arc evaporation sources and sputtering evaporation sources are respectively combined, a film forming apparatus in which a plurality of arc evaporation sources and sputtering evaporation sources are arranged in the same film forming chamber is known.

For example, an apparatus and a method for forming a hard film by a sputtering evaporation source after switching the arc evaporation source or the sputtering evaporation source, operating the arc evaporation source, stopping the arc evaporation source after introducing the metal ion etching by the arc evaporation source, and introducing the process gas Has been proposed (see US Pat. No. 5,234,561).

Moreover, the film-forming apparatus provided with the magnetic field application mechanism in the arc evaporation source and the sputtering evaporation source is also proposed (refer European patent publication No. 0403552 and US patent 6,232,003). In addition, Fig. 7 of US Pat. No. 6,232,003 discloses, as a prior art, the effects of mutual interference between the respective magnetic fields of the arc evaporation source and the sputtering evaporation source which do not have a magnetic field application mechanism.

It is also known to simultaneously form an arc evaporation source and a sputtering evaporation source to form a hard film, or to add a third element to the film to refine the crystal grains of the film, or to improve characteristics such as wear resistance. For example, by adding Si or B to a TiAlN film such as a TiN film or a cutting tool, it has been proposed to improve oxidation resistance and to increase hardness by miniaturization of crystal grains (US Pat. No. 5,580,653, US Pat. No. 5,318,840). Publication, KH Kim et al. Surf.Coat.Technol. 298 (2002) 243-244, 247). In addition, a method of improving the wear resistance by adding B to the CrN film used for the sliding member by using the piston ring of an automobile as a representative and increasing the hardness is also proposed (see US Patent No. 6,232,003).

Even in a hard film whose crystal structure mainly consists of a rock salt structure type, when the crystal grain diameter (hereinafter also referred to as crystal grain size) of the rock salt structure hard film becomes coarse depending on the film formation conditions, there is a limit in improving wear resistance due to high hardness. .

In addition, all the said prior art adds a specific element uniformly in a film, and forms a single layer film which consists of a single chemical composition. The film thus formed is hardened by miniaturization of the crystal grains constituting the film, thereby improving wear resistance.However, the friction coefficient on the surface of the film is insufficient to improve the wear resistance and lubricity. There is room for further improvement, including the aggressiveness of the furnace.

In addition, hard films formed by these conventional methods and means do not necessarily have sufficient performance for cutting tools and sliding parts that are increasingly demanded, and further improvement in durability such as wear resistance is required.

For example, in the method of adding an element such as Si or B to the wear resistant film to refine the crystal grains of the film, the degree of crystal grain refinement is determined according to the amount of the element added, and only by changing the addition amount of the particle diameter of the film Control is possible. Therefore, in order to produce the film of a different particle diameter, it is necessary to produce two or more target which changed the addition amount of an element. For this reason, the preparation of the sample of the particle diameter suitable for the purpose, ie, the film | membrane which has the characteristic according to the objective, has become a very complicated practical problem, and there exists a limit to the improvement of abrasion resistance of the hard film actually obtained.                         

In addition, when the arc evaporation source and the sputtering evaporation source are operated simultaneously in the same film formation chamber as in the above-described conventional apparatus, even if the arc evaporation source or the sputtering evaporation source is operated alternately and operated, depending on the hard film material and the film forming conditions, It is difficult to avoid problems in film formation such as a dense hard film or a hard film having a desired composition, or an abnormal discharge during the film forming operation. For this reason, it is a fact that there was a limit also in the improvement of abrasion resistance by the hardening of the obtained hard film.

For example, when forming a nitride hard film such as TiN, TiCN or TiAlN, the film is formed in a mixed gas atmosphere of Ar and nitrogen to form nitride. However, in the same film formation chamber, emission electrons from the arc evaporation source and the sputtering evaporation source are easily induced to the side of the chamber which becomes the anode as in the substrate. As a result, the concentration of emitted electrons decreases, and there is less collision with the sputtering gas or the reactive gas, and it is difficult to ionize the gas with high efficiency.

In addition, an inert sputtering gas such as Ar (argon), Ne (neon), Xe (xenon) is used as the sputtering evaporation source, and a reactive gas (reactive gas) such as nitrogen, methane, acetylene is used as the arc evaporation source. For this reason, when arc film formation and sputtering film formation are performed simultaneously in the same film formation chamber, especially when film formation is carried out by increasing the partial pressure of a reactive gas such as nitrogen in order to improve the film performance, the material used for the sputtering evaporation source. In some cases, the sputtering target material reacts with the reaction gas to generate an insulator (insulator) on the surface of the target material, and this insulator is likely to cause abnormal discharge (arking) in the sputtering evaporation source. This problem also hinders high efficiency gas ionization.

In this way, when ionization of the gas at high efficiency is inhibited, ion irradiation to the substrate cannot be strengthened, densification of the hard coat layer can not be achieved, and the surface properties such as roughening of the surface are also reduced. As a result, in the conventional film forming apparatus, especially when the arc evaporation source and the sputtering evaporation source are operated at the same time in the same film forming chamber, there is a big limitation in high characteristics such as high hardness of the hard film and high performance.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in such a way that the crystal grain diameter of the rock salt-structure hard film is refined to improve the characteristics such as the wear resistance of the hard film, a hard film having better wear resistance and lubricity than a conventional hard film, An object of the present invention is to provide a hard laminated film having excellent wear resistance and oxidation resistance. In addition, it is an object of the present invention to provide a composite film forming apparatus and a sputtering evaporation source capable of obtaining a hard film having desired characteristics without causing a problem in film formation when the arc evaporation source and the sputtering evaporation source are simultaneously operated in the same film formation chamber.

In order to achieve the above object, the structure of the hard laminated film of the present invention, that is, the structure of the hard laminated film common to the first to fourth inventions of the present invention as described below is alternately laminated with layers A and B made of a specific composition. The crystal structure of layer A is different from that of layer B, the thickness of layer A per layer is at least twice the thickness of layer B per layer, and the thickness of layer B per layer is at least 0.5 nm, The thickness of layer A per layer is 200 nm or less.

The gist of the hard laminated film of the first invention for achieving the above object is a fine film having a film structure in which a hard film layer A having a cubic rock salt structure and a hard film layer B having a crystal structure other than the cubic rock salt structure are alternately laminated. It is a crystalline hard film.

In the first aspect of the present invention, by forming a laminated structure by combining two hard coating layers having different crystal structures as described above, the crystal grain diameter of the hard coating layer A having a cubic rock salt crystal structure as a main phase is simply and arbitrarily selected. Fine control.

That is, when the hard coating layer A of a cubic rock salt crystal structure is formed into a hard coating layer B of a crystal structure which does not have a cubic rock salt structure, alternatingly and sequentially (stacking), it is the lower layer in this hard film layer B part. Crystal growth of the hard film layer A to be stopped once. In addition, when film formation (lamination) of the hard coat layer A is carried out, new crystal growth of the hard coat layer A is started from the hard coat layer B. Therefore, the crystal grain diameter of the hard coat layer A can be finely controlled.

On the other hand, when the film is formed by stacking only the hard film layer A without the hard film layer B, or when the hard film layers A having the same cubic rock salt crystal structure are laminated with each other even if the components are different, the crystals of the hard film layer A are formed. Growth does not stop and continues to grow. As a result, it becomes easy to become coarse crystal grain diameter.

In the first aspect of the invention, by miniaturizing the crystal grains of the hard coat layer A, it is possible to obtain excellent characteristics not found in the conventional hard coat such as high hardness of the hard coat and improvement of wear resistance.

2nd invention of this invention WHEREIN: The composition of the layer A and the layer B in the hard laminated film of the said structure is as follows, respectively.

Layer A: (Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e

In the above, X is one or two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si, 0≤α≤ 0.9, 0≤ a≤ 0.15 , 0 ≤ b ≤ 0.3, 0 ≤ c ≤ 0.1, 0.2 ≤ e ≤ 1.1 (α represents an atomic ratio of X, and a, b, and c represent atomic ratios of B, C, and O, respectively). .

Layer B: B _1-st C _s N _t

In the above, 0 ≤ s ≤ 0.25, (1-s-t) / t ≤ 1.5 (s, t represents the atomic ratio of C, N, respectively.

Or Si _1-xy C _x N _y

In the above, 0 ≤ x ≤ 0.25, 0.5 ≤ (1-x-y) / y ≤ 1.4 (x, y represents the atomic ratio of C, N, respectively.

Or C _1-u N _u

In the above, 0 ≦ u ≦ 0.6 (u represents an atomic ratio of N. The same applies hereinafter).

In said 2nd invention, said (alpha) can be made into 0.

In said 2nd invention, said (alpha) can be made 0.05 or more.

In the second invention, the layer A has a rock salt cubic structure, and diffraction from the (111) plane and the (200) plane observed in the X-ray diffraction pattern obtained by the θ-2θ method using CuKα rays. At least one of the half widths of the lines may be 0.3 ° or more.

According to the second aspect of the invention, a high hardness A layer and a B layer having lubricity are alternately laminated on the surface of the substrate to suppress and refine the growth of the crystal grains constituting the A layer, thereby providing more excellent wear resistance and lubricity than conventional hard coatings. It is possible to provide a hard coating and a method of manufacturing the same.

The gist of the hard laminated film according to the third aspect of the present invention is that in the hard laminated film having the above structure, the layer A is composed of the formula (1), and the layer B is represented by the formulas (2), (3), (4) and (5). It is made of a composition selected from any one of the compositions.

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

[In the above, x, y, a, b, c each represent an atomic ratio, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, M is a metal element selected from at least one of 4A, 5A, 6A and Si]

B _1-xy C _x N _y

[In the above, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, B / N ≦ 1.51]

Si _1-xy C _x N _y

[Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, 0.5 ≦ Si / N ≦ 2.0]

C _1-x N _x

[Wherein, x represents an atomic ratio and 0 ≦ x ≦ 0.6]

Cu _1-y (C _x N _1-x ) _y

[Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.5]

In the third aspect of the invention, as in the above-described aspect, the hard film is a laminated structure in which layers A and B formed of specific compositions are alternately laminated so that the compositions of these layers A and B are different from each other.

In addition, these layers A which are laminated with each other are composed of a specific composition of (TiAlM) (BCNO) system, and these layers B are composed of (BCN) system, (SiCN) system, (CN) system, and Cu (CN) system. It is set as the specific composition chosen from either.

As a result, for example, the wear resistance and the oxidation resistance can be significantly improved as compared with the hard film composed of a single composition such as the layer A or the hard film composed of the lamination of the layer A.

The gist of the hard laminated film according to the fourth aspect of the present invention is that in the hard laminated film having the above structure, layer A is composed of any one of the following formulas (1) and (6), and layer B is of the following formula (7). .

Formula 1

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

[In the above, x, y, a, b, c each represent an atomic ratio, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, M is a metal element selected from at least one of 4A, 5A, 6A, and Si]

(Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e

[In the above, α, a, b, c, and e represent an atomic ratio, respectively, 0 ≦ α ≦ 0.9, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3,0 ≦ c ≦ 0.1, 0.2 ≦ e ≦ 1.1, In addition, X is a metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, Si]

M _1-d M1 _d (B _a C _b N _1-abc O _c )

[In the above, M is a metal element selected from any one or more of W, Mo, V, Nb, M1 is selected from one or more of 4A, 5A, 6A, Si, excluding the W, Mo, V, Nb. The metal elements, a, b, c, and d, respectively, represent an atomic ratio, and 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and 0 ≦ d ≦ 0.3].

According to the fourth invention, for example, the wear resistance and the oxidation resistance can be significantly improved as compared with the hard film composed of a single composition such as the layer A or the hard film composed of the lamination of the layer A.

In addition, the gist of the preferred method for forming the hard laminated film of the first to fourth aspects of the present invention is a method of forming the microcrystalline film with a film forming apparatus provided with at least one arc evaporation source and one sputtering evaporation source each having a magnetic field applying mechanism. The components of the hard coating layer A are evaporated at the arc evaporation source, the components of the hard coating layer B are evaporated at the sputtering evaporation source, and the hard coating layers A and B are alternately laminated on the substrate.

Summary of the Invention The fifth aspect of the composite film forming apparatus of the present invention for achieving the above object is a film forming apparatus in which at least one arc evaporation source and a sputtering evaporation source each having a magnetic field applying mechanism are disposed in the same film forming chamber, and the substrate to be deposited is formed using the arc The magnetic field applying mechanism is configured to have a means for sequentially moving relatively between the evaporation source and the sputtering evaporation source, and to form magnetic lines of force between adjacent evaporation sources during film formation.

Another aspect of the composite film forming apparatus of the present invention for achieving this object is a film forming apparatus in which one or more arc evaporation sources and sputtering evaporation sources each having a magnetic field applying mechanism are arranged in the same film forming chamber, wherein the substrate to be formed is deposited on the arc evaporation source. And a means for sequentially moving relatively between the sputtering evaporation sources, during the film formation, the sputtering gas is introduced from the vicinity of the sputtering evaporation source, and the reaction gas is introduced from the vicinity of the arc evaporation source.

In addition, the gist of the sputtering evaporation source of the sixth invention of the present invention for achieving this object is to use an electrically insulating material in a portion other than the erosion region as the sputtering evaporation source used for the composite film forming apparatus.

Similarly, another aspect of the sputtering evaporation source of the sixth invention of the present invention is a sputtering evaporation source for use in the composite film forming apparatus, and has a shield at a portion other than the erosion region which becomes a floating potential or a ground potential with respect to the potential of the sputtering target. will be.

In the composite film forming apparatus of the fifth aspect of the invention, the magnetic field applying mechanism is configured such that the magnetic force lines of the adjacent evaporation sources are connected to each other during the film formation, as described in the above-mentioned.

For this reason, the magnetic lines of force in the same film formation chamber are in a closed state (closed magnetic field structure), and as described later, the electrons emitted from the evaporation source are easily trapped in the closed magnetic field structure and easily become an anode as a substrate. Not induced. As a result, even when arc film formation and sputtering film formation are performed simultaneously in the same film formation chamber, the concentration of emitted electrons increases, collisions with sputtering gas and reactive gas increase, and gas can be ionized with high efficiency.

In the composite film forming apparatus of the fifth aspect of the invention, as in the other aspect described above, sputtering gas is introduced from the vicinity of the sputtering evaporation source and film reaction gas is introduced from the vicinity of the arc evaporation source during film formation. For this reason, even when arc film formation and sputtering film formation are performed simultaneously in the same film formation chamber, and especially when film formation is carried out by increasing the partial pressure of reactive gas such as nitrogen to improve the film performance, such as nitrogen to the sputtering gas, etc. Mixing of the reaction gases is unlikely to occur, an insulating film is formed on the target surface by the ionized mixed gas, and the problem of abnormal discharge is suppressed. For this reason, gas can be ionized with high efficiency.

By promoting ionization of the gas at high efficiency according to each of the fifth and sixth inventions, or combinations thereof, ion irradiation to the substrate can be enhanced, and high characteristics such as high hardness due to the densification of the hard coating layer can be achieved. Can be achieved. Moreover, abnormal occurrence in film formation, such as abnormal discharge, can also be suppressed.

In addition, as in the above two aspects of the sputtering evaporation source of the sixth aspect of the present invention, the particles sputtered from the erosion region react with nitrogen on the non-erosion region by preventing voltage from being applied to the non-erosion region of the sputtering evaporation source. It is not reacted, combined with gas, and deposited. As a result, abnormal discharge resulting from excitation can be prevented and gas can be ionized with high efficiency.

First, an embodiment is described below with respect to the requirements of the hard film of the present invention.

First, the method of particle size control common to the inventions of the first to third embodiments will be described.

(Control of Grain Size of Hard Film Layer A)

The conventional hard coating layer A, such as TiN, CrN or TiAlN, which is widely used for cutting tools and wear-resistant sliding parts formed by sputtering or ion plating, is shown schematically in FIG. Similarly, after nucleation occurs on the substrate, the columnar particles tend to grow in width while growing in a columnar shape.

On the other hand, for example, in the case of the first invention, as shown in Fig. 1, the growth pattern of the coating crystal is typically selected as a hard coating layer B, and a coating having a crystal structure having no cubic rock salt structure is selected. Lamination (film formation) is carried out alternately. In this case, growth of the hard coat layer A is stopped once by inserting each hard coat layer B, and each hard coat layer A repeats nucleation and growth from above each hard coat layer B. For this reason, compared with the said FIG. 2, the crystal grain diameter of the film thickness direction and the direction parallel to a board | substrate (horizontal direction) is refine | miniaturized. 1 and 2 show simplified drawings of the TEM observation of 45,000 times the cross section of the hard to laminated film.

For example, when the TiAlN film is selected as the hard coating layer A and the SiN film is selected as the hard coating layer B, the cross-sectional TEM of the TiAlN / SiN laminated film in the case where the above laminated structure is produced with the thickness of the layer A as about 50 nm and the thickness of the layer B as about 5 nm. As a result, the growth of crystal grains in the film thickness direction was interrupted for each layer, and the crystal grains were refined as compared with FIG. By refinement | miniaturization of such crystal grains, the outstanding characteristic which a conventional film | membrane, such as high hardness of a film | membrane, is obtained can be obtained.

In the second invention, the layer A becomes crystalline (Cr ₂ N type or CrN type), and the layer B becomes amorphous. In this way, two layers having different crystal states are alternately stacked to form a film, whereby the grains of the layer A are interrupted in the thickness direction of the film by insertion of the layer B, and the crystals having the same thickness as the layer A are crystallized. You will stay at the particle size. As a result, the crystal grains become finer as compared with the case where there is no interruption of the growth of the crystal grains as in the prior art, and the hardness of the film further increases.

Next, the laminated constitution requirements of the two types of hard coating layers common to the first to fourth inventions will be described.

(Thickness of hard laminated film)

The film thickness of the whole hard laminated film of this invention differs in the necessity according to the use of cutting tools, sliding parts, etc. In the case of a cutting tool, about 1-5 micrometers in general, and in the case of a sliding member, about 3-100 micrometers are standard. Therefore, it is preferable to control the film thickness by changing the number of layers after determining the thickness of layers A and B, respectively, on the basis of the following description so as to be the thickness of these hard laminated films.

(Relationship between the film thickness of layer A and the film thickness of layer B)

In the hard laminated film of this invention, the thickness of the layer A per layer shall be 2 times or more of the thickness of the layer B per layer. Layer A, which is a columnar of the hard laminated film of the present invention, mainly defines properties such as high hardness, wear resistance, and high oxidation resistance required for the hard laminated film of the present invention. When the layer A becomes a thin thickness less than twice the thickness of the layer B, the properties of the layer B become dominant in the properties of the hard laminated film and do not satisfy the above required properties. For this reason, the thickness of the layer A is made 2 times or more of the layer B thickness.

For example, in the case of the first invention, the hard coating layer A having a cubic rock salt structure is basically a columnar having abrasion resistance, and the hard coating layer B having a crystal structure other than the cubic rock salt structure has a hard coating layer even though it is hard. It is lower than A. Therefore, in order to have excellent abrasion resistance as a hard film, it is necessary to secure a thickness in which the properties of the hard film layer A having a cubic rock salt structure dominate as a hard film.

(Film thickness of layer A)

The thickness (film thickness) of the layer A per layer is 200 nm or less, preferably 100 nm or less, more preferably 50 nm or less. When the thickness of the layer A per layer becomes thicker than these upper limits, such as less than 200 nm, there is no composite effect as a laminated film, and there is no big difference from the case where only layer A is laminated and formed without a layer B. As a result, the properties of layer A alone are only expressed, and layer B cannot supplement the properties of layer A.

For example, in the first invention, when the thickness of the layer A per layer exceeds 200 nm, the effect of grain refinement is low, and there is no great difference from the case where only the hard coat layer A is laminated without the hard coat layer B and formed into a film. Before the hard coating layer B is provided, crystal growth of the hard coating layer A occurs to easily cause coarse crystal grain diameters. Therefore, there is a possibility that the characteristics of the hard film grown without interrupting the conventional crystal growth become equivalent.

In addition, it is preferable that the thickness of the layer A per layer shall be 2 nm or more. If the thickness of the layer A is less than 2 nm, even if the number of layers A is increased, there is a possibility that the characteristics of the layer A cannot be secured as a hard laminated film.

(Film thickness of layer B)

The thickness of the layer B per layer is 0.5 nm or more, preferably 1 nm or more. The thickness of the layer B also varies depending on the thickness of the layer A, but in the case of thicknesses below these lower limits such as less than 0.5 nm, there is no great difference from the case where only the layer A is laminated without a layer B and formed into a film. As a result, the properties of layer A alone are only expressed, and layer B cannot supplement the properties of layer A.

For example, in the case of the first invention, when the thickness of the hard coat layer B is less than 0.5 nm, there is a possibility that the thickness of the layer B is so thin that the effect of stopping grain growth on the layer A of the layer B is lost. For this reason, the possibility that the crystal grain of the hard coat layer A will not refine | miniaturize also arises.

On the other hand, it is preferable that the upper limit of the thickness of the layer B per layer shall be 1/2 or less of the thickness of the layer A. When the thickness of the layer B exceeds 1/2 of the thickness of the layer A, when the thickness of the layer A is thinned, the properties of the entire hard laminated film are large, affecting the layer B, and the characteristics of the layer A are difficult to be exhibited. There is a possibility of quality.

In addition, the thickness of layer A and layer B can be calculated | required as an average value of the value measured from each of the two visual fields of 50-50 million times magnification by observation by cross-sectional TEM.

(Lamination Mode of Hard Coating Layer A and Hard Coating Layer B)

As a constitution of the layer of the hard laminated film of the present invention, when the compositions of the layers A and B are basically different from each other, alternating lamination between layers A and B (layer A / layer B / layer A / layer B) (layer It is preferable to laminate (multilayer) a plurality of (multiple) units of A / layer B) as one unit. However, layer A / layer A / layer B / layer B or layer A / layer B / layer B / layer A, layer B / layer B / layer A / layer A, layer B / layer A / layer A / layer B, Etc. as one unit, these units can be combined, respectively, and can be laminated | stacked alternately. In addition, it is not necessary to make these laminated layers A and B mutually the same composition. That is, within the scope of the present invention, the compositions of the layers A and the layers B to be laminated according to the purpose may be different from each other, such as, for example, the layer A1 / layer B1 / layer A2 / layer B2. For example, in the first to third inventions, a hard coating layer (different material) having the same crystal structure (for example, cubic rock salt structure) as layer A but having a different component composition is selected as the third hard coating layer (C). Then, the hard coating layer C is interposed therebetween, for example, layer A / layer B / layer C or layer B / layer A / layer B / layer C, etc. as one unit, and these units are combined, respectively, and a lamination is carried out. You can also carry out. In addition, the lamination number of these units can select arbitrary lamination numbers, such as 20-1000, according to the thickness of the hard laminated film made into the above objective.

Next, the composition of each of the hard coat layers A and B of the first to fourth inventions will be described.

[This first invention]

(Component Composition of Hard Coating Layer A)

The component composition of the hard coating layer A, which is the columnar of the hard coating of the present invention, should take a rock salt structure crystal structure and select a material having high hardness and wear resistance. In this respect, as a hard film having a rock salt-type crystal structure, for example, a cubic crystal containing any one of Ti, Cr, Al, and V, such as TiN, CrN, or TiAlN, which are widely used for cutting tools and wear-resistant sliding parts. Compounds of any one of nitride, carbonitride and carbide having a rock salt structure can be applied. Moreover, in addition to these, it is applicable as long as it is a compound of 4A, 5A, 6A, and the element chosen from 1 or more types of Al, Si, and the element chosen from 1 or more types of B, C, N. All of these compounds have a cubic rock salt structure as the crystal system, and have high hardness and excellent wear resistance. In addition, within a range in which the crystal structure of the hard coating layer A maintains a rock salt structure, a small amount of oxygen is added to the layer A in an amount of 10% or less (0.1 or less in atomic ratio) to add the hard coating layer A to 4A, 5A, 6A and Al. , An oxynitride or an acid carbonitride layer of an element selected from one or more of Si, or a layer containing these oxynitrides or acid carbonitrides, and the properties may be improved accordingly. It is included in the scope of the invention.

The chemical formulas of compounds applicable to these hard coat layers A are Ti (C _1-x N _x ), Cr (C _1-x N _x ), V (C _1-x N _x ) in the _{primary system} , where x is Value of 0-1, the same below], etc. can be shown. In binary systems, TiAl (C _1-x N _x ), TiSi (C _1-x N _x ), TiCr (C _1-x N _x ), TiV (C _1-x N _x ), TiB (C _1-x N _x ), CrAl (C _1-x N _x ), CrSi (C _1-x N _x ), CrV (C _1-x N _x ), CrB (C _1-x N _x ), VAl (C _1-x N _x ), VSi (C _1-x N _x ), VB (C _1-x N _x ), and the like.

In ternary systems, TiAlSi (C _1-x N _x ), TiAlCr (C _1-x N _x ), TiAlV (C _1-x N _x ), TiAlB (C _1-x N _x ), TiCrSi (C _1-x N _x ), TiCrV (C _1-x N _x ), TiCrB (C _1-x N _x ), TiVSi (C _1-x N _x ), TiVB (C _1-x N _x ), CrAlSi (C _1-x N _x ), CrAlV (C _1-x N _x ), CrAlB (C _1-x N _x ), CrSiV (C _1-x N _x ), CrSiB (C _1-x N _x ), CrVB (C _1-x N _x ), VAlSi (C _{1 -x} N _x ), VAlB (C _{1 -x} N _x ), or the like.

TiAlSiCr (C _1-x N _x ), TiAlSiV (C _1-x N _x ), TiAlSiB (C _1-x N _x ), TiAlCrV (C _1-x N _x ), TiAlCrB (C _1-x N _x ), TiAlVB (C _1-x N _x ), TiCrSiV (C _1-x N _x ), TiCrSiB (C _1-x N _x ), TiCrVB (C _1-x N _x ), CrAlSiV (C _1-x N _x ), CrAlSiB (C _1-x N _x ), CrAlVB (C _1-x N _x ), CrSiVB (C _1-x N _x ), VAlSiB (C _1-x N _x ), and the like.

Moreover, among these compounds, the compound containing any one of Ti, Cr, or Al is higher hardness. As this compound, compounds, such as TiN, TiCN, TiAlN, CrN, TiCrAlN, CrAlN, are illustrated. In particular, the compound containing Al is excellent in oxidation resistance, and is suitable for cutting tool applications in which this oxidation resistance is particularly required. Moreover, compounds containing Cr (for example, CrN, TiCrN, CrCN) are suitable for mechanical parts use.

Generally, the hard film of the crystal structure of rock salt structure type can be measured and analyzed by X-ray diffraction by the (theta) -2 (theta) method. The hard coating of the rock salt structure type has high peak intensity on the (111) plane, the (200) plane, and the (220) plane in this X-ray diffraction, respectively. For example, a hard film such as (TiAl) (CN) has a rock salt structure crystal structure, and Al is substituted at the Ti site of TiN of the rock salt structure to form a complex nitride of the rock salt structure. In this case, since the AlN (lattice constant 4.12 kPa) of the rock salt structure is a high temperature and high pressure phase and is a high hardness material, when the ratio of Al in (TiAl) (CN) is increased while maintaining the rock salt structure, the hardness of the (TiAl) (CN) film is increased. Can be further increased.

(Component Composition of Hard Coating Layer B)

The hard coat layer B is an element selected from at least one of 4A, 5A, 6A, and Al, and at least one of B, C, and N, of the crystal structure in which the hard coat layer B does not have a cubic rock salt structure, respectively. Selected from compounds (hexagonal crystals, etc.) with an element selected from (2) selected from nitrides, carbonitrides, carbides of elements selected from one or more of B, Si, Cu, Co, Ni, and C, or (3) It is preferable to select from metal Cu, metal Co, and metal Ni. Among these, the said (2) group is especially preferable.

As the hard coat layer B, the above-mentioned grain refinement effect can be expressed as long as it is a substance having a crystal structure which does not basically have a rock salt cubic structure. However, in the case where the hard coating of the present invention is used in high temperature of a cutting tool or the like or in consideration of the required characteristics as a sliding part, the material of each of the above groups having heat resistance and wear resistance is preferable. Among them, BN, BCN, SiN, SiC, SiCN, B-C or Cu, CuN, CuCN, or metal Cu, which is a compound containing B or Si, is suitable among the above (2) groups.

[This second invention]

The inventors of the present invention obtain a hard film having excellent wear resistance and lubricity by forming a layer A having a chemical composition satisfying the following formula (8) and a layer B having a chemical composition satisfying the following formula (9) to satisfy the above-described lamination configuration requirements. It was found that the present invention was completed.

Layer A: Cr (B _a C _b N _1-abc O _c ) _e

0≤ a≤ 0.15, 0≤ b≤ 0.3, 0≤ c≤ 0.1, 0.2≤ e≤ 1.1

Layer B: B _1-st C _s N _t

0≤ s≤ 0.25, (1-s-t) / t≤ 1.5

Below, the reason which prescribed | regulated the composition and thickness of layer A and layer B as mentioned above is demonstrated concretely.

[Composition of Layer A]

First, the layer A is made of a Cr (B, C, N, O) film, and the ratio of B, C, N, O is set to the ratio shown in the above formula (1) for the following reason. That is, the layer A is a composition whose main component is to maintain the abrasion resistance to the film, the high hardness of chromium nitride (CrN, Cr ₂ N). And, by adding C, B, and O to chromium nitride, the hardness is further increased and wear resistance is improved, but since excessive addition of these elements leads to a decrease in hardness, the upper limit of a (i.e., B) is 0.15, preferably The upper limit of b (ie, C) is 0.3, preferably 0.2, and the upper limit of c (ie, O) is 0.1, preferably 0.07 or less.

Further, the ratio e of the total of B, C, N, O of the Cr is preferably in a range of 0.2 to 1.1, and this range is the structure of the crystals constituting the layer A is a Cr ₂ N structure, or CrN structure It corresponds to the range of composition. In addition, the crystal structure of layer A can be confirmed by cross-sectional TEM and electron beam diffraction as mentioned later.

[Composition of Layer B]

Next, since layer B provides lubricity to a film, it is set as the BN compound which functions as a solid lubricant. Here, in order to form a BN compound, the ratio (1-s-t) / t of B and N needs to be 1.5 or less, and preferably 1.2 or less. In addition, by adding C to the BN compound, it is possible to achieve high hardness while giving lubricity to the layer B. However, the excessive addition causes the upper limit of s to be 0.25 because the lubricity is lost while the hardness decreases. Preferably the ratio s / (1-s-t) of C to B is 0.25 or less, more preferably 0.1 or less.

[Modification of Layer A Composition]

As described above, the layer A is a layer having high hardness and abrasion resistance, and further improves characteristics by miniaturization of grains by inserting the layer B. Substituting with another element raises the hardness of layer A further, and can further improve abrasion resistance.

Recommended as the other element is one or two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si. Among them, Al, Si, W, and Ti are preferable as one element, and each combination of Al and Si, Al and Ti, W, Si, Ti, and Si is preferable as two elements.

If the substitution ratio α to the other element is too large, the ratio of the original Cr decreases and the hardness synergistic effect is lost. Although the lower limit is not specifically limited in substitution ratio (alpha), In order to acquire a fixed effect by substitution with the said other element, it is preferable to set it as 0.05 or more. Although the more preferable range of substitution ratio (alpha) changes also with kinds and combination of elements to substitute, generally 0.4-0.8 are standard.

In addition, in the case of replacing Cr with two elements of Ti and Al, if the Al is increased, the oxidation resistance of the film is improved. Therefore, the ratio of Al is preferably higher than the ratio of Ti. Since the film is likely to become amorphous, the ratio of Al to the total amount of Cr, Ti, and Al is preferably 0.8 or less.

In addition, when Si is contained in a substitution element, when there is too much ratio of Si, layer A will become amorphous, It is preferable to make the ratio of Si with respect to the total amount of Cr and a substitution element 0.5 or less.

[Modification of Layer B Composition]

Even if a SiCN-based or CN-based coating is used in addition to the BCN coating as the layer B, a coating having excellent abrasion resistance can be obtained.

When the SiCN-based coating is used for the layer B, in general, the low friction coefficient similar to that of the BCN-based coating cannot be obtained and the aggression to the counterpart cannot be reduced, but since the hardness is higher than that of the BCN-based coating, the wear resistance of the coating itself is improved. This becomes a film suitable for a cutting tool or the like that does not need to consider the aggressiveness to the counterpart. In addition, the oxidation resistance is also excellent. In addition, when C is excessively added, the hardness decreases, so the upper limit of the addition ratio of C is 0.6.

In addition, since the CN-based coating is unstable at a high temperature, it cannot generally be used in a high-temperature sliding motion environment, but as a standard, a sliding motion environment of 400 ° C. or lower can exhibit a sliding motion characteristic equivalent to that of a BCN-based film. The standard of the addition ratio of N is 0.6 or less, Preferably it is 0.4 or less.

[Degree of Refinement of Grain of Layer A]

The layer A may have a hexagonal Cr ₂ N-type structure or a hexagonal rock salt-type CrN-type structure according to the ratio of the total amount of Cr and B, C, N, and O as described above, but the wear resistance is higher for the CrN-type structure. Since it is excellent, it is set as rock salt cubic crystal structure as a preferable form of the crystal structure of layer A.

Further, the present invention is directed to laminating the layers A and B at the ratio of the film thickness and the film thickness shown above, whereby the growth of the grains of the layer A is stopped in the layer B, and as a result, the refinement of the grains occurs. I am doing it.

Here, the degree of refinement of the crystal grains can be evaluated using the full width half maximum (FWHM) of the diffraction lines from the (111) plane and the (200) plane of the rock salt cubic structure of the layer A observed by the X-ray diffraction pattern as an index. have. In general, the half width of the diffraction line has a constant relationship with the crystal grain size of the material to be measured, and the half width of the diffraction line increases as the crystal grain diameter decreases. However, it is known that the half width of the diffraction line also depends on other factors such as nonuniform stress generated in the film, and the relationship between the half width and the crystal grain size is not necessarily linearly proportional.

Based on these, the present inventors examined the relationship between the half width of the diffraction line and the film hardness or wear resistance. It was found that the properties were further improved. More preferably, the lower limit of the half width is 0.4 degrees. The upper limit of the half width is not particularly limited, but is substantially about 1 °.

In the present invention, the half width of the diffraction line was evaluated by X-ray diffraction by the θ-2θ method using CuKα rays (40 kV · 40 mA). As other X-ray optical system conditions, divergence, scattering slits were 1 °, light receiving slits were 0.15 mm, and the light receiving slits before the counter were 0.8 ° and scanning speed was 2 ° / min (continuous using a graphite monochromator). Scan) and step width 0.02 degrees.

[This third invention]

(Component Composition of Layer A)

The component composition of the layer A, which is the columnar of the hard laminated film of the present invention, needs to have a high oxidative property, particularly for applications in which sliding parts such as cutting tools become hot. In addition, the layer A needs to have basic characteristics such as high hardness and wear resistance required for the hard coating.

For this reason, as a component composition of layer A, what consists of the following formula (1) is preferable.

Formula 1

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

[In the above, x, y, a, b, c each represent an atomic ratio, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, M is a metal element selected from at least one of 4A, 5A, 6A and Si]

Among the compositions represented by the formula (1) of the layer A, in particular, (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ) [where x, y, a, b, and c are the atomic ratios, respectively. Represents a value of 0.5 ≦ x ≦ 0.8, 0.05 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and M is a metal element selected from one or more of Cr, V, and Si. It is preferable that the composition is made of.

In the above formula (1), the atomic ratio between (TiAlM) and (BCNO), in other words, the atomic ratio between the two parentheses between the metal element group and the nonmetal element group is usually 1: 1, but is necessarily 1: 1. It is not limited only to. In the Ti-based compound actually formed as described below, the atomic ratio between (TiAlM) and (BCNO) is naturally not limited to 1: 1 only, depending on the difference in film forming conditions and the like, for example, 0.8 to 1.2: 0.8 to It has a deflection width of 1.2. Therefore, in the above formula (1), the atomic ratio between (TiAlM) and (BCNO) and the atomic ratio between the metallic element group and the nonmetallic element group naturally allow the deflection width of the atomic ratio of the Ti-based compound to be actually formed. .

(Ti-based component)

In the component composition of this layer A, first, nitrides, carbonitrides, borides, and carbonitrides of Ti are hardened as hard films, as represented by Ti-based compounds such as TiAlN, TiAlCrN, TAlVN, TiAlNbN, TiAlBN, TiAlCrCN, and the like. Moreover, it has characteristics, such as high abrasion resistance, and is optimal as a component used as a base of the layer A part of this invention.

(Al)

By containing Al with respect to this Ti type component like the said component composition formula, the hardness and oxidation resistance of layer A improve. This effect is particularly exhibited when Al is included in the atomic ratio x in the range of 0.4 to 0.8 (the range of 0.4 ≦ x ≦ 0.8), preferably in the range of 0.5 to 0.8 (the range of 0.5 ≦ x ≦ 0.8). . On the other hand, even if it contains Al, if it deviates from this component range, there is no or little improvement effect of hardness and oxidation resistance, so there is no meaning of including Al.

(Metal element M)

As in the above component composition formula, when the metal element selected from any one or more of 4A, 5A, 6A, and Si represented by M is selectively contained, the hardness and the oxidation resistance of the layer A are further improved. This effect is particularly exhibited when the metal element M is contained in an atomic ratio y of 0.6 or less (in the range of 0 ≦ y ≦ 0.6). This is because when M is contained in an atomic ratio exceeding 0.6, the total content of Ti and Al serving as a base is less than 0.4 in atomic ratio, and both the hardness and the oxidation resistance of the layer A are rather lowered.

The metal element M exhibiting the above effects is preferably a combination selected from one or more of Cr, V, and Si, and the preferred content ranges exhibiting the above effects of these metal elements range from 0.05 to 0.6 in atomic ratio y. (0.05 ≤ y ≤ 0.6), more preferably in the range of 0.1 to 0.3 (0.1 ≤ y ≤ 0.3).

(Nonmetallic element)

Nitrogen (N is essential to form nitrides, carbonitrides, borosilicates, and carbonitrides of the nonmetallic elements selected from B, C, and N in the compositional formula of the layer A. The content of nitrogen is contained in other selectively contained B The content of C (the value of a or b in the component composition formula) or the content of O (the value of c in the component composition formula) is defined as N ₁ -abc as in the component composition formula of the layer A.

Boron (B) is optionally contained to form borosilicates and carbonitrides. However, even if it contains too much, the soft B compound precipitates and both the hardness and the oxidation resistance of the layer A are reduced. For this reason, the upper limit is 0.15 (the above 0 <a≤0.15) by the atomic ratio a, Preferably the upper limit is 0.1 or less (0 <a <0.1).

Carbon (C) is optionally contained to form carbides and carbonitrides. However, excessive addition also leads to softening of the layer A, thereby lowering both the hardness and the oxidation resistance of the layer A. For this reason, an upper limit is made 0.3 (the said 0 <= b <= 0.3) by the atomic ratio b, Preferably, an upper limit is made 0.2 or less (0 <b <0.2).

In addition, about the oxygen (O), although the hardness of the layer A can be increased by containing a trace amount, when it contains more than 0.1 by atomic ratio (c), the ratio of the oxide to a film will increase, The toughness of the film is impaired. The upper limit is made 0.1 or less (0 <c <0.1) at this point.

(Component Composition of Layer B)

Layer B basically has a role of imparting properties that layer A does not have, or further improving the properties of layer A. For this reason, in this invention, when laminating | stacking alternately with layer A, it selects by each characteristic of a composition, an objective, from each compound represented by four composition formulas of following General formulas 2-5.

Formula 2

B _1-xy C _x N _y where x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, B / N ≦ 1.5]

Formula 3

Si _1-xy C _x N _y , wherein x and y each represent an atomic ratio, and 0 ≦ x ≦ 0.25, 0.5 ≦ Si / N ≦ 2.0]

Formula 4

C _1-x N _x where x represents an atomic ratio and 0 ≦ x ≦ 0.6]

Formula 5

Cu _1-y (C _x N _1-x ) _y [where x and y each represent an atomic ratio, 0 ≦ x ≦ 0.1 and 0 ≦ y ≦ 0.5]

Each compound represented by the above four formulas has a crystal structure different from that of the above-mentioned compound of layer A, and by laminating these compounds with layer A, the grain splitting effect of the grains of layer A is brought about, resulting in miniaturization of grains. It becomes possible to plan. As a result, the hardness of the hard laminated film can be significantly increased.

Of the compounds represented by the above four formulas, in the case where both the nitride or carbonitride-based compound of formula (B) of formula (2) and the carbon or carbon nitride compound of formula (4) are laminated with layer A, lubricity is not present in layer A. You can give it. Among them, the B-based compound of formula (2) is stable at high temperatures, and excellent in lubricating properties at room temperature to high temperatures. In addition, the C-based compound of Formula 4 is superior to the B-based compound of Formula 2 in terms of lubricating properties at low temperatures. The above formula (composition range) of the B-based compound of Formula (2) and C-based compound of Formula (4) is a composition range necessary for ensuring lubricity.

In the above formula (2) of the B-based compound, in securing this lubricity, the atomic ratio x of the amount of C is 0.25 or less (the above 0 ≦ x ≦ 0.25), preferably 0.2 or less. In addition, in the case of the B rich compound in which B / N in the general formula (2) exceeds 1.5, it does not have a lubricating property. Therefore, the upper limit of the ratio of B / N of B / N is 1.5 or less (The said B / N <= 1.5), More preferably, it is 1.2 or less (B / N <= 1.2). In the formula (2), since the atomic ratio y of the amount of nitrogen is determined from the ratio of B and N in the overlap with the amount of C, the range cannot be determined by y alone. That is, when the amount of C is determined, since the individual amount of B and N from B / N is determined including y, it is not necessary to determine the range by y alone only if the range of B / N is determined.

The Si-based compound of formula (3), which is a nitride or carbonitride-based compound of Si, has an effect of further improving oxidation resistance by combining with layer A. In the general formula (3), when the amount of C (atomic ratio x) is large, the hardness of the coating tends to be lowered. Therefore, the upper limit of the atomic ratio x of C is 0.25 or less (where 0 ≦ x ≦ 0.25), more preferably 0.2 It is assumed as (0 ≦ x ≦ 0.2). In addition, the ratio of Si / N of Si / N is defined to deviate from the range in which the Si / N ratio is defined (the above 0.5 ≦ Si / N ≦ 2.0), more preferably 0.5 ≦ Si / N ≦ 1.4, and the hardness This is because the reduction is remarkable, which deteriorates the hardness characteristics of the entire laminated film. In addition, since the atomic ratio y of the amount of nitrogen in the general formula (3) is determined from the ratio of Si and N in the overlap with the amount of C, y alone cannot determine the range. That is, when the amount of C is determined, since the individual amounts of Si and N from Si / N are determined including y, it is not necessary to determine the range by y alone only if the range of Si / N is determined.

The atomic ratio x of the amount of C in the general formula (4) of the carbon or carbon nitride compound deteriorates lubricity when excessively contained in excess of 0.6. Therefore, the upper limit of the atomic ratio x of the amount of C is set to 0.6 or less (where 0 ≦ x ≦ 0.6).

Compounds of the general formula (5), which are nitrides or carbonitride-based compounds of Cu, can be increased in hardness by combining with the layer A within a prescribed composition range. If the upper limit of the atomic ratio x of C exceeds 0.1 or the atomic ratio y of the (C _x N _1-x ) _y exceeds 0.5, such as when combined with the layer A, the hardness increase effect There is no. Therefore, x and y are each set to 0 ≦ x ≦ 0.1 and 0 ≦ y ≦ 0.5 as described above.

[This fourth invention]

(Component Composition of Layer A)

The component composition of the layer A, which is the columnar of the hard laminated film of the fourth aspect of the present invention, needs to have a high oxidative property, particularly for applications in which sliding parts such as cutting tools become hot. In addition, the layer A needs to have basic characteristics such as high hardness and wear resistance required for the hard coating. For this reason, as a component composition of layer A, it selects from the compound of the specific composition of Ti system or Cr system.

(Ti-based compound)

Of these, the Ti-based layer A is composed of the following formula (1).

Formula 1

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ) [where x, y, a, b, c each represent an atomic ratio, and 0.4 ≦ x ≦ 0.8, 0 ≦ y ≤ 0.6, 0 ≤ a ≤ 0.15, 0 ≤ b ≤ 0.3, 0 ≤ c ≤ 0.1, and M is a metal element selected from one or more of 4A, 5A, 6A, and Si]

In the above formula (1), the atomic ratio between (TiAlM) and (BCNO), in other words, the atomic ratio between the two parentheses between the metal element group and the nonmetal element group is usually 1: 1, but is necessarily 1: 1. It is not limited only to. In the Ti-based compound actually formed as described below, the atomic ratio between (TiAlM) and (BCNO) is naturally not limited to 1: 1 only, depending on the difference in film forming conditions and the like, for example, 0.8 to 1.2: 0.8 to It has a deflection width of 1.2. Therefore, in the above formula (1), the atomic ratio between (TiAlM) and (BCNO) and the atomic ratio between the metallic element group and the nonmetallic element group naturally allow the deflection width of the atomic ratio of the Ti-based compound to be actually formed. .

In the component composition of this layer A, first, the nitride, the carbonitride, the boride, and the carbonitride of Ti are hard films, as represented by Ti-based compounds such as TiAlN, TiAlCrN, TiAlVN, TiAlNbN, TiAlBN, TiAlCrCN, and the like. It has characteristics such as high hardness and high wear resistance, and is optimal as a component serving as the base of the layer A portion of the present invention.

By containing Al with respect to this Ti-based component like the said component composition formula, the hardness and oxidation resistance of layer A improve. This effect is particularly exhibited when Al is included in the atomic ratio x in the range of 0.4 to 0.8 (the range of 0.4 ≦ x ≦ 0.8), preferably in the range of 0.5 to 0.8 (the range of 0.5 ≦ x ≦ 0.8). . On the other hand, even if it contains Al, if it is out of this component range, there is no effect of improving the hardness and oxidation resistance, or it is not meant to include Al.

(Metal element M)

As in the above component composition formula, when the metal element selected from any one or more of 4A, 5A, 6A, and Si represented by M is selectively contained, the hardness and the oxidation resistance of the layer A are further improved. This effect is particularly exhibited when the metal element M is contained in an atomic ratio y of 0.6 or less (in the range of 0 ≦ y ≦ 0.6). This is because when M is contained in an atomic ratio exceeding 0.6, the total content of Ti and Al serving as a base is less than 0.4 in atomic ratio, and both the hardness and the oxidation resistance of the layer A are rather lowered.

The metal element M exhibiting the above effects is preferably a combination selected from one or more of Cr, V, and Si, and the preferred content range exhibiting the effects is in the range of 0.06 to 0.6, more preferably 0.1 in atomic ratio. To 0.3.

(Nonmetallic element)

Nitrogen in the nonmetallic elements selected from B, C, and N in the compositional formula of the layer A (N is essential to form nitrides, carbonitrides, borides, and carbonitrides. The content of C (the value of a or b in the component composition formula) or the content of O (the value of c in the component composition formula) is defined as N ₁ -abc as in the component composition formula of the layer A.

Boron (B) is optionally contained to form borosilicates and carbonitrides. However, even if it contains too much, the soft B compound precipitates and both the hardness and the oxidation resistance of the layer A are reduced. For this reason, the upper limit is 0.15 (the above 0 <a≤0.15) by the atomic ratio a, Preferably the upper limit is 0.1 or less (0 <a <0.1).

Carbon (C) is optionally contained to form carbides and carbonitrides. However, excessive addition also leads to softening of the layer A, thereby lowering both the hardness and the oxidation resistance of the layer A. For this reason, an upper limit is made 0.3 (the said 0 <= b <= 0.3) by the atomic ratio b, Preferably an upper limit is 0.2 or less (the said 0 <b <0.2).

In addition, about the oxygen (O), although the hardness of the layer A can be increased by containing a trace amount, when it contains more than 0.1 by atomic ratio (c), the ratio of the oxide to a film will increase, The toughness of the film is impaired. The upper limit is made 0.1 or less (0 <c <0.1) at this point.

(Cr-based compound)

In addition, Cr-based layer A is made of the composition of the following formula (6).

Formula 6

(Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e

[In the above, α, a, b, c and e each represent an atomic ratio, 0 ≦ α ≦ 0.9, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, 0.2 ≦ e ≦ 1.1, X is a metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si.]

In the Cr-based component composition of the layer A, nitrides, carbonitrides, borides, and carbonitrides of Cr are also high hardness as hard films as represented by Cr-based compounds such as CrN, Cr ₂ N, CrSiN, CrAlN, CrBN, CrSiBN, etc. It has the characteristics of high abrasion resistance, etc., and is optimal as a component used as a base of the layer A part of this invention.

This Cr-based component composition has a lower hardness than the Ti-based component composition when the amount of Cr is small. However, when used for a sliding member, it has a characteristic of having low aggression with respect to a counterpart compared with Ti-based component composition, and is preferable for a sliding member. In addition, even if the amount of Cr is small, high hardness can be obtained depending on the added element, and is suitable for cutting tools.

(Additional element X)

The additional element X for this high hardness is a specific metal element selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, Si. It is especially exhibited when these metal elements X are included in 0.9 or less (the range of said 0 <=== 0.9) in atomic ratio (alpha). This is because when the metal element X is contained in an atomic ratio of more than 0.9, the base content of Cr is less than 0.1 in an atomic ratio, and both the hardness and the oxidation resistance of the layer A are rather lowered.

In particular, when used for a sliding member, it is necessary to secure a certain amount of Cr because a small amount of Cr increases the aggressiveness to the counterpart. For this reason, when using it for a sliding member, Preferably the said atomic ratio (alpha) is 0.5 or less, More preferably, it is 0.3 or less, and ensures Cr amount. Moreover, when using for a cutting tool, on the contrary, Preferably, the said atomic ratio (alpha) is made 0.5 or more, More preferably, it makes 0.7 or more, and raises hardness.

(Nonmetallic element)

The prescribed values and meanings of the nonmetallic elements selected from B, C and N in the component composition formula of the layer A are the same as those of the Ti-based compound. However, the atomic ratio (e) of (B _a C _b N ₁ -abc O _c ) _e in Chemical Formula 6 is in the range of 0.2 to 1.1 (the above 0.2 ≦ e ≦ 1.1). If e is less than 0.2, the amount of nonmetallic elements selected from B, C, and N is insufficient, and both the hardness and the oxidation resistance of the layer A are lowered. On the other hand, even if e exceeds 1.1, metal elements, such as Cr and X, run short, and both hardness and oxidation resistance of layer A fall rather.

(Component Composition of Layer B)

The layer B basically has a role of imparting characteristics such as lubricity at high temperatures that the layer A does not have, or further improving characteristics of the layer A, such as oxidation resistance. This property is exerted when layer B consists of the composition of the following formula (7).

Formula 7

M (B _a C _b N _1-abc O _c )

[In the above, M is a metal element selected from any one or more of W, Mo, V, Nb, a, b, c each represents an atomic ratio, 0≤ a≤ 0.15, 0≤ b≤ 0.3, 0≤ c≤0.1]

In the above formula (7), the atomic ratio between M and (BCNO), in other words, the atomic ratio between the metal element M and the nonmetallic group is usually 1: 1, but is not necessarily limited to 1: 1. Is the same as in the case of formula (1). Therefore, the atomic ratio between the metal element M and the nonmetallic element group allows deflection widths such as 0.8 to 1.2: 0.8 to 1.2 and the like.

The compound represented by the above formula (7) has a crystal structure different from that of the compound of the Ti-based or Cr-based specific composition of the layer A. For this reason, the characteristic of layer A can be improved, for example, the hardness of a hard laminated film is increased significantly.

That is, the compound of the layer A usually has a cubic rock salt crystal structure and, depending on the content of the element, has a lattice constant of about 0.41 to 0.43 nm. In contrast, the compound including W, Mo, V, and Nb represented by the formula of Formula 7 has a relatively large lattice constant of 0.44 nm or more. For this reason, when lamination | stacking (film-forming) with the compound of said layer A using these compounds as layer B, a big deformation | transformation is introduce | transduced into the interface of layer A and layer B. As a result, even when the film is deformed from the outside of the film when the film is in use, and the crack of the film or the like goes up and down (thickness direction) of the film, there is a high probability that the crack of the film is blocked by the deformation of the interface. . For this reason, it is estimated that it will improve characteristics, such as hardness and durability of the layer A, as mentioned above.

Of the compounds represented by the formula of Formula 7, the compound containing W, Mo, and Nb, when laminated with the layer A, can improve the oxidation resistance of the layer A. Compounds containing W, Mo, and Nb have a low oxidation start temperature in the monoliths of 600 to 700 ° C. However, in the case of lamination with a layer A having a thickness not less than twice the thickness of the layer B, the elements of W, Mo, and Nb are diffused in the oxide film formed by Ti, Al, Cr, and the like contained in the layer A to form the oxide film. Densification, and as a result, the oxidation resistance of layer A is improved.

Of the compounds represented by the formula of Formula 7, the compound containing V does not improve the oxidation resistance of the layer A, but can improve the lubricity at a high temperature of the layer A. V forms an oxide (V ₂ O _5, etc.) that is soft at high temperatures, so that the oxide improves lubricity at high temperatures of layer A.

In the composition formula of the above formula (7), in the case of containing two or more of these W, Mo, V, and Nb, it is preferable to appropriately select the composition ratio necessary for achieving the above-mentioned effect.

The prescribed numerical value and meaning of the nonmetallic element of (B _a C _b N _1-abc O _c ) in the composition formula of Formula 7 are the same as in the case of A layer described above. In other words, nitrogen (N) is essential to form nitrides, carbon nitrides, borosilicates, and carbonitrides. This nitrogen content is different from the component composition formula of the said layer B by content of B and C which are selectively contained (value of a or b in the said component composition formula), or O content (value of c in the said component composition formula). _Likewise , N _{1 -abc} is defined.

Boron is optionally contained to form borosilicate, carbonitride. However, even if it contains excessively, soft B compound will precipitate, and both the hardness and oxidation resistance of layer B, and also A will fall. For this reason, the upper limit is 0.15 (the above 0 <a≤0.15) by atomic ratio a, Preferably the upper limit is 0.1 or less (0 <a <0.1).

Carbon (C) is optionally contained to form carbides and carbonitrides. However, even if it contains too much, it will lead to soft nitriding of layer B, and also layer A, and it will reduce both the hardness and the oxidation resistance of a film. For this reason, an upper limit is made 0.3 (the said 0 <= b <= 0.3) by the atomic ratio b, Preferably, an upper limit is made 0.2 or less (0 <b <0.2).

In addition, the oxygen (O) may be able to increase the hardness of the layer B, and further, the layer A, by containing a small amount of the oxygen (O). The ratio increases, and the toughness of the film is impaired. The upper limit is made 0.1 or less (0 <c <0.1) at this point.

(Substitution by other metal element M1 of metal element M of layer B)

In the composition formula 3 of the layer B, the metal element M is replaced with a metal element M1 selected from at least one of 4A, 5A, 6A, and Si, except for W, Mo, V, and Nb. It may be. This means that the inclusion of the metal element M1 is allowed within the range that does not impair the effect of the metal element M and the properties of the metal element M1 selected for the layer B depending on the combination with the metal element M by containing the metal element M1. There is a meaning that the addition or the performance of the layer B (and further, the layer A or the film) can be improved.

For example, the film hardness can be improved by replacing W, Mo, and V as the metal element M with any one of Ti, Al, Si, and Cr as the metal element M1.

In the quantitative ratio of _1-b M _b M1 in the case of these substituted, and the atomic ratio (b) in the range of 0.3 or less (wherein 0≤ b≤ 0.3). When the metal element M1 is substituted by more than 0.3 in the atomic ratio b, rather, the effect of improving the hardness and durability of the layer A of W, Mo, Nb, and V, which is the metal element M, and the effect of improving the oxidation resistance of W, Mo, and Nb B, the high temperature lubricity improvement effect of Nb is inhibited.

EMBODIMENT OF THE INVENTION Below, embodiment is concretely demonstrated using drawing for the composite film-forming apparatus of this 5th invention suitable for manufacture of the hard laminated film of this invention of 1st-4th. 5 is a plan view showing an embodiment of the film forming apparatus of the present invention. 6 is a top view which shows the film-forming apparatus of a comparative example. 8 is a front view showing another embodiment of the composite film forming apparatus of the present invention. 9 is a plan view showing another embodiment of the composite film deposition apparatus of the present invention.

In the film forming apparatus shown in FIGS. 5 and 6, a plurality of substrates 1 (four symmetrically in FIG. 5) are placed on the rotating plate 9 in the chamber 8 in a common manner, and are circumferential (circumferential) around them. Therefore, the sputtering evaporation sources 2 and 3 and the arc evaporation sources 5 and 6 are arranged so as to face the sputtering evaporation sources 2 and 3 and the arc evaporation sources 5 and 6, respectively. The sputtering evaporation source and the arc evaporation source are alternately arranged to be adjacent to each other.

Each board | substrate 1 is rotated with the rotation of the rotating plate 9, and the board | substrate 1 alternately passes through the arc evaporation source 5 and 6 and the sputtering evaporation source 2 and 3 front. In this case, the arc evaporation sources 5 and 6 and the sputtering evaporation sources 2 and 3 may be rotated around the substrate 1 without rotating the rotating plate 9 or the substrate 1. What is necessary is just to have the means to move the film-forming board | substrate relatively sequentially between the said arc evaporation source and a sputtering evaporation source.

In another aspect, the arcing sputtering evaporation sources 2 and 3 and the arc evaporation sources 5 and 6 are arranged in series in a straight line or the like, without arranging the cylinder evaporation sources 5 and 6 in the circumferential shape. It is also possible to sequentially move relatively between the evaporation source and the sputtering evaporation source.

In the case where a hard film such as TiAlN is formed by using the arc evaporation sources 5 and 6, for example, a reactive gas such as nitrogen, methane or acetylene is introduced into the chamber 8 to generate a reactive gas of about several Pa. Film formation is performed using a TiAl target in the atmosphere of the pressure range containing the TiAl target.

In addition, when forming a hard film, such as TiAlN, using the sputtering evaporation source 2 and 3 similarly, the point which uses TiAl target is the same as that of film-forming by an arc. However, inert gases such as Ar, Ne, and Xe, which become sputtering gases, are mixed with a reaction gas with nitrogen and the like, and the total pressure of the atmosphere is carried out in a pressure region lower than film formation by an arc of about 0.1 Pa.

The rotating plate 9 is rotated, and the respective substrates 1 are rotated so that the substrates 1 pass alternately in front of the arc evaporation sources 5 and 6 and the sputtering evaporation sources 2 and 3. Film formation or film formation by each arc can be carried out sequentially, and a hard film of the same or different composition or thickness can be sequentially formed into multiple layers on the substrate 1 using the same or different hard materials.

(Magnetic field authorization mechanism)

Here, the film deposition apparatus shown in Figs. 5 and 6 is commonly generated by a magnetic field applying mechanism 4 such as a permanent magnet which the arc evaporation sources 5 and 6 and the sputtering evaporation sources 2 and 3 each have, respectively. And the magnetic field 10 to be controlled.

However, in the case of using this magnetic field 10, in the film forming apparatus of the present invention shown in Fig. 5, the magnetic fields 10 of the adjacent evaporation sources, for example, the magnetic field between the arc evaporation source 5 and the sputtering evaporation sources 2 and 3, respectively. (1) They are connected to each other. In other words, the magnetic field applying mechanism 4 is configured such that the magnetic field lines (magnetic field 10) of the evaporation sources adjacent to each other during the film formation are connected to each other.

For this reason, the magnetic field 10 (magnetic field line) in the same film forming chamber 8 is in a closed state (closed magnetic field mechanism), and the electrons emitted from the evaporation source are trapped in the closed magnetic field structure, similarly to the substrate 1. It is not easily guided to the chamber 8 which becomes the anode. As a result, the concentration of the emitted electrons increases, collisions with the sputtering gas and the reactive gas increase, and the gas can be ionized with high efficiency.

As a result, even when arc film formation and sputtering film formation are simultaneously performed in the same film formation chamber, in the film forming apparatus of the present invention of FIG. 1, the directivity of ions from both of the adjacent evaporation sources is improved, and ion irradiation to the substrate 1 is performed. It is possible to form a film having more excellent properties by increasing.

In contrast, in the film forming apparatus of Comparative Example of FIG. 6, the magnetic fields 10 of the two evaporation sources adjacent to each other, for example, the magnetic fields 10 of the arc evaporation source 5 and the sputtering evaporation sources 2 and 3 do not connect to each other and are independent of each other. have.

For this reason, the magnetic field 10 (magnetic field line) in the same film-forming chamber 8 is in an open state (individual field structure), and the emission electrons from the evaporation source are quick to follow the direction of each magnetic field 10 (magnetic field line). Is easily guided to the chamber 8. As a result, when arc film formation and sputtering film formation are performed simultaneously in the same film formation chamber, the concentration of emitted electrons is reduced, so that collision with the sputtering gas and the reactive gas is reduced, so that the gas ionization efficiency is lowered.

Therefore, in the film forming apparatus of the comparative example of FIG. 6, the directivity of the ions from both evaporation sources is moderate, and the amount of ion irradiation to the substrate is reduced, which increases the possibility of impairing the film characteristics or the film forming efficiency.

(Backed by increased ion count)

The ion current flowing through the substrate 1 was measured using the film forming apparatus shown in FIGS. 5 and 6. In the film-forming apparatus of this invention of FIG. 5, the ion current of about 14 mA / cm <^2> flowing through the board | substrate 1 was obtained, and the ion current flowing to the board | substrate 1 clearly increased. In contrast, in the film forming apparatus of the comparative example of FIG. 6, the ion current flowing in the substrate 1 was about half that of about 7 mA / cm ² , and the ion current flowing in the substrate 1 did not increase. Also from these results, it is supported by the film forming apparatus of the present invention that the ion irradiation to the substrate can be increased to form a film having better characteristics.

(Other Embodiments of Film Forming Apparatus)

Next, another embodiment of the film forming apparatus of the present invention will be described with reference to FIG. 8. In the film forming apparatus shown in FIG. 8, as shown in FIG. 5, the sputtering evaporation sources 2 and 3 and the arc evaporation sources 5 and 6 are alternately arranged in series in the chamber 8 without being arranged circumferentially. The arrangement method of each evaporation source may be curved, etc., although it is not necessarily linear, and the number of arrangement of each evaporation source can also be selected freely.

Also in the case of the film forming apparatus of the present invention shown in Fig. 8, the substrate 1, the arc evaporation sources 5 and 6 and the sputtering evaporation sources 2 and 3, which are the object to be processed, are relatively moved by appropriate means, so that the substrate 1 is moved. The arc evaporation sources 5 and 6 and the sputtering evaporation sources 2 and 3 are alternately passed. Then, in the atmosphere containing the reactive gas in the chamber 8, the components of the hard coat layer are evaporated using the arc evaporation sources 5 and 6, and the components of the hard coat layer are respectively evaporated using the sputtering evaporation sources 2 and 3, respectively. , The hard coating layer and the hard coating layer are alternately and sequentially laminated on the substrate 1 to form the desired hard coating.

And also in the film-forming apparatus of this invention of FIG. 8, the magnetic fields 10 of both the adjacent evaporation sources, for example, the magnetic field 10 of the arc evaporation source 5 and the sputtering evaporation sources 2 and 3 are mutually connected. . That is, the magnetic field applying mechanism 4 is configured so that the lines of magnetic force between the evaporation sources adjacent to each other during film formation are connected to each other. For this reason, the magnetic field 10 in the same film-forming chamber 8 is in a closed state (closed magnetic field mechanism), and the emission electrons from the evaporation source are trapped in this closed magnetic field structure and become an anode as in the substrate 1. It is not easily guided to the chamber 8. As a result, similarly to the film forming apparatus of the present invention of FIG. 5, the concentration of emitted electrons increases, collisions with sputtering gas or reactive gas increase, and gas can be ionized with high efficiency.

Nitrogen partial pressure

In the film forming apparatus of the present invention as described above with reference to FIGS. 5 and 8, when the arc evaporation source and the sputtering evaporation source are operated simultaneously to form a hard film containing nitrogen, nitrogen is mixed in the sputtering gas and the mixed nitrogen It is preferable to make partial pressure 0.5 Pa or more.

As described above, the atmospheric gas conditions and the pressure conditions differ greatly in the film formation by arc and the film formation by sputtering. For this reason, K. H. Kim et al. Surf. Coat. In Technol et al., For example, when a hard film such as TiSiN is formed by simultaneously operating an arc evaporation source and a sputtering evaporation source, the ratio of the reaction gas such as Ar and nitrogen, which becomes the sputtering gas, is 3: 1, and the total pressure is 0.08 Pa. The film is formed by evaporating Ti with an arc evaporation source and Si with a sputtering evaporation source with a partial pressure of nitrogen of about 0.02 Pa.

However, when the film is formed under such conditions, since the partial pressure of nitrogen to be mixed is too low, the addition of nitrogen into the hard film is insufficient, and the macroparticles in the hard film also increase. For this reason, a dense film becomes difficult to complete.

On the other hand, in order to sufficiently add nitrogen to the hard film, to suppress the generation of large particles in the hard film, and to form a film having a high surface property with a high density, the partial pressure of nitrogen mixed in the sputtering gas is as described above. It is preferable to set it as 0.5 Pa or more.

The influence of this nitrogen partial pressure was investigated for the case where the hard film of TiAlCrN was formed by simultaneously operating the arc evaporation source and the sputtering evaporation source using the film forming apparatus shown in FIG. 3. The TiAl alloy (Ti 50: Al 50) was evaporated as the arc evaporation source, and Cr was evaporated at the same time as the sputtering evaporation source, and was formed by varying the ratio of nitrogen as the reactive gas and nitrogen as the reactive gas (nitrogen partial pressure). And about each example, nitrogen content (atomic%) in a hard film, the surface roughness (Ra), and the Vickers hardness (Hv) of a hard film were measured.

The results of arranging these in relation to the nitrogen partial pressure are shown in FIGS. 10 to 12. 10 shows the relationship between the nitrogen partial pressure and the nitrogen content in the hard film, FIG. 11 shows the relationship between the nitrogen partial pressure and the surface roughness Ra of the hard film, and FIG. 12 shows the relationship between the nitrogen partial pressure and the Vickers hardness of the hard film, respectively. .

As can be seen from FIG. 10, there is a clear difference in the nitrogen content in the hard film at a nitrogen partial pressure of 0.5 Pa. That is, in the region where the nitrogen partial pressure was less than 0.5 Pa, the nitrogen content in the hard coating was almost monotonous and was significantly reduced compared with the region where the nitrogen partial pressure was 0.5 Pa or more. In contrast, in the region where the nitrogen partial pressure is 0.5 Pa or more, the nitrogen content in the hard coating is stable, maintaining a high level of about 50 atomic%.

As can be seen from FIG. 11, there is also a clear difference in the surface roughness Ra of the hard film at a nitrogen partial pressure of 0.5 Pa. That is, the surface roughness Ra of a hard film rises rapidly to about 0.38 micrometer in the area | region whose nitrogen partial pressure is less than 0.5 Pa. In contrast, in the region where the nitrogen partial pressure is 0.5 Pa or more, the surface roughness Ra of the hard film is almost stable, and is maintained at a low level of 0.1 m or less.

Moreover, as can be seen from FIG. 12, there is a clear difference in the Vickers hardness of the hard film at the nitrogen partial pressure of 0.5 Pa. That is, the Vickers hardness was significantly reduced to the level of 1100 Hv in the region where the nitrogen partial pressure was less than 0.5 Pa. On the other hand, in the region where nitrogen partial pressure is 0.5 Pa or more, the Vickers hardness of the hard film is stable and maintains a high level of about 2500 Hv.

From these results, the partial pressure of nitrogen mixed in the sputtering gas is set to 0.5 Pa or more in order to sufficiently add nitrogen to the hard coating to suppress the generation of large particles in the hard coating and to form a film having a high surface quality with high density. You can see the meaning of doing. These results and trends also apply to other hard films such as TiN, TiCN, or TiAlN other than the investigated TiAlCrN.

(Problem of abnormal discharge by insulator formation)

In the film formation using only the above-mentioned nitrogen partial pressure of 0.5 Pa or more, when arc deposition and sputtering film formation are performed simultaneously in the same film formation chamber, different problems may occur depending on the material used for the sputtering evaporation source. In other words, the sputtering target material reacts with the reaction gas to generate an insulator (insulator) on the target material surface, and this insulator may cause abnormal discharge (arking) in the sputtering evaporation source. For example, when Si is used as a target material and sputtered in nitrogen, Si easily reacts with nitrogen to form an insulator of SiN on the surface of the target material, and the above abnormal discharge problem is particularly likely to occur.

Moreover, even when such an insulator does not generate | occur | produce or when a sputtering target material reacts with a reaction gas and a compound generate | occur | produces on the surface of a target material, the evaporation rate in a sputtering evaporation source may fall by the compound layer of this surface. In addition, these problems also become a factor of inhibiting ionization of the gas with high efficiency.

Conventionally, in order to solve such a problem, the partial pressure of the reaction gas such as nitrogen to the inert sputtering gas is kept low, the reaction between the reaction gas such as nitrogen and the sputtering target material is suppressed, and the sputtering of the target material by the sputtering gas It was supposed to occur first.

K. H. Kim et al., Supra. Surf. Coat. In Technol et al., When a hard film such as TiSiN is formed by simultaneously operating an arc evaporation source and a sputtering evaporation source, it is for this reason that as described above, the partial pressure of the reaction gas such as nitrogen with respect to Ar or the like as the sputtering gas is lowered. There is also.

However, as described above, in the case of film formation using the film forming apparatus of FIG. 5 or 6, the composition of the atmosphere and the pressure region differ greatly in arc film formation and sputtering film formation. For this reason, when the film is formed by simultaneously operating the arc evaporation source and the sputtering evaporation source that require a relatively high pressure, it is necessary to increase the partial pressure of the reactive gas such as nitrogen to the sputtering gas, even in view of the above-described film performance. The chances are high.

(Introduction method of atmosphere gas)

This problem can be dealt with during the film formation by introducing a sputtering gas into the chamber from the vicinity of the sputtering evaporation source and introducing a reaction gas into the chamber from the vicinity of the arc evaporation source. This aspect is shown in FIG. Although the basic structure of the film-forming apparatus of this invention of FIG. 9 is the same as that of FIG. 5 mentioned above, it is characteristic that during sputtering, sputtering gas is introduce | transduced from the said sputtering evaporation source vicinity, and the reaction gas is introduce | transduced from the said arc evaporation source vicinity.

More specifically, the film forming apparatus of FIG. 9 introduces sputtering gas from the vicinity of the sputtering evaporation sources 3 and 4 by the conduit 12 and the branch pipes 12a and 12b during film formation. The reaction gas is also introduced from the vicinity of the arc evaporation sources 5 and 6 by the conduits 11 and the branch pipes 11a and 11b.

Accordingly, in the vicinity of the sputtering evaporation sources 3 and 4, the partial pressure of the reaction gas such as nitrogen to the inert sputtering gas is kept low, and the reaction between the reactive gas such as nitrogen and the sputtering target material is suppressed, thereby sputtering Sputtering of the target material by gas can be made to occur preferentially.

On the other hand, the ratio (nitrogen partial pressure) of nitrogen used as a reaction gas with respect to sputtering gas in the whole atmosphere in a chamber can be raised in the said film performance improvement. In addition, in the vicinity of the arc evaporation sources 5 and 6, the pressure of the reactive gas can also be increased depending on the film forming conditions by the arc.

Even when the introduction of these atmospheric gases is used in combination with the magnetic field applying mechanisms described above with reference to FIGS. 5 and 9 or used alone, mixing of reactive gases such as nitrogen in an inert sputtering gas is less likely to occur, resulting in ionization. The problem that the insulating film is formed on the target surface by the mixed gas thus formed and abnormal discharge occurs is suppressed. For this reason, gas can be ionized with high efficiency.

(Problem of abnormal discharge due to magnetic field formation)

In addition, abnormal discharge in a sputtering target may generate | occur | produce for another cause other than formation of the insulator of the surface of a target material by reaction gas, such as said nitrogen.

This can also be said to be a problem peculiar to sputtering control by a magnetic field such as the magnetic field applying mechanism 4 described above. This problem will be described in detail with reference to Figs. 13A and 13B. 14A and 14B show detailed structures of the sputtering evaporation sources 2 and 3, and FIG. 13A is a plan view of only the target material 20 in the sputtering evaporation sources 2 and 3, and FIG. 13B is a view of the sputtering evaporation sources 2 and 3. Front view. In Fig. 13B, reference numeral 4 denotes a magnetic field applying mechanism, 13 denotes a shield of the target material 20, 15 denotes a ground earth of the shield 13, 14 denotes a backing plate of the target material 20, Reference numeral 16 denotes a sputtering power supply and 17 a jig for setting the target material 20.

As shown in FIG. 13B, the magnetron sputtering evaporation sources 2 and 3 using the magnetic field form a horizontal magnetic field 10 on the surface of the target material 20, intentionally trapping electrons as described above, and thus the electron density. To increase the ionization of the sputtering gas to increase the sputtering efficiency.

In this case, the erosion region 21 and the non-erosion region 22 inevitably occur on the target material 20 surface shown in FIG. 13A. In the erosion region 21, which is an oblique portion, a lot of ions of the sputtering gas are generated, so that the electron density is high, so that sputtering is preferentially performed. On the contrary, sputtering hardly occurs in the non-erosion region 22 of the center portion of the target material 20 and the peripheral portion of the erosion region 21. For this reason, in the non-erosion area | region 22, the particle | grains sputtered from the erosion area | region 21 react with the reaction gas, such as nitrogen, and are easy to deposit. For this reason, this deposit may become an insulator (insulating film) on the surface of the target material, which may cause a problem of abnormal discharge.

Sputtering Evaporation Source

In order to solve this problem, it is preferable to prevent voltage from being applied to the non-erosion region 22 of the sputtering evaporation source during film formation.

As one means for this, a material which is electrically insulated is used for the portion of the non-erosion region other than the erosion region 21 of the sputtering evaporation source. 14A and 14B illustrate this embodiment, and the basic configuration of the apparatus is the same as that of FIGS. 13A and 13B. In FIGS. 14A and 14B, the non-erosion region 23 at the center of the target material 20 and the periphery of the erosion region 21 is made of an insulator 23 using an electrically insulating material. . As such a material, use of heat resistance BN (boron nitride), alumina, etc. which can withstand the heat generated in the sputtering evaporation source is preferable.

FIG. 15 similarly discloses an example in which a non-erosion region is provided with a shield, which has a shield which becomes a floating potential or a ground potential with respect to the potential of the sputtering target in a portion other than the erosion region. have.

15A and 15B, the basic configuration of the apparatus is the same as that of FIGS. 13A and 13B. 15A and 15B, the non-erosion region 25 at the center of the target material 20 is provided with a shield that becomes a floating potential. In addition, the non-erosion region 24 at the periphery of the erosion region 21 is provided with a shield (connected with the ground earth 15) that becomes a ground potential.

In the aspects of Figs. 9 and 10 of the above-described configuration in which the non-erosion region 22 is not energized, particles sputtered from the erosion region 21 form nitrogen on the non-erosion region 23. It does not react and bond with reaction gases, such as these, and accumulate. Therefore, occurrence of the above abnormal discharge problem is prevented.

Next, the formation method of the hard laminated film of this 1st-4th invention is demonstrated.

First, the problem in the formation method and its solution which are common to this invention of 1st-4th are demonstrated.

As a method for forming the hard laminated film of the first to fourth inventions, for example, as shown in FIG. 3, each of the hard coat layers A and B is formed on the substrate 1 by combining a plurality of sputtering evaporation sources 2 and 3. There is a way to form. In this case, for example, the hard coat layer A component is deposited on the substrate 1 as the evaporate 2a from the sputtering evaporation source 2 and the hard coat layer B component is used as the evaporate 3b from the sputtering evaporation source 3. do.

In addition, as shown in FIG. 4, there is a method of forming each of the hard coat layers A and B on the substrate 1 using the plurality of electron beam evaporation sources 5 and 6. Forming method; In this case, for example, the hard coat layer A component is used as the evaporate 5a from the electron beam evaporation source 5 by the electron beam 7 as the evaporate 6b from the electron beam evaporation source 6 by the electron beam 7. The coating layer B component is deposited on the substrate 1.

However, in the present invention, as shown in FIG. 5 described above, the components of the hard coat layer A are evaporated using the arc evaporation source, and the components of the hard coat layer B are respectively evaporated using the sputtering evaporation source and viewed in an atmosphere containing a reactive gas. The method of forming the film of this invention is the most preferable. The arc evaporation source and the sputtering evaporation source are arranged in combination, and the substrate is sequentially moved or passed through these arc evaporation source and the sputtering evaporation source, so that the components of the hard coating layer A by the arc evaporation source and the components of the hard coating layer B by the sputtering evaporation source. The film forming method of laminating alternately and sequentially on a substrate has the following advantages over the film forming methods of FIGS. 3 and 4 above.

In particular, arc evaporation has a faster deposition rate than sputter evaporation. For this reason, by depositing the components of the hard coat layer A by the arc evaporation source, it is possible to form the layer A which requires a film thickness of about five times or more that of the layer B at high speed. In addition, since the sputtering evaporation source is easier to adjust the deposition rate than the arc evaporation source and operates with a very small input power (for example, 0.1 kW), the sputtering evaporation source has a characteristic of accurately controlling the thickness of the film layer of the thin film such as layer B.

In addition, by combining the characteristics of these arc evaporation and sputtering evaporation, the ratio of the thickness of the layer A and the layer B is set in a preferable range by the ratio of the input power of the arc evaporation source and the sputtering evaporation source, and then the rotation speed of the substrate (rotation) Speed, movement speed) can be arbitrarily determined for the repetition period of the layer A + layer B. In addition, the thickness of the layer A can be arbitrarily set (that is, the crystal grain diameter in the present invention of the first to the third).

The actual embodiment will be described below with respect to the method of forming the hard laminated film of the first invention (film formation method).

The reason why it is preferable to use the apparatus of FIG. 5 is demonstrated using the case where TiN is used as layer A and SiN is used as layer B as an example. In the case of the combination of the sputtering evaporation sources 2 and 3 shown in FIG. 3, a method of using TiN and SiN as a target and a mixed gas atmosphere of Ar of a sputtering gas and nitrogen of a reactive gas using Ti and Si as targets The method of performing sputtering alternately can be considered. The thickness of each of the layers A and B is possible by controlling the deposition time using the operating time of the respective sputtering evaporation source or the shutter in front. However, in the sputtering method, since the film formation speed is slow, it takes time to form the layer A, which requires about five times the film thickness of the layer B, and is not efficient.

In the case where the electron beam evaporation shown in Fig. 4 is used, Ti and Si are dissolved in the electron beam evaporation sources 5 and 6, respectively, to form layers A and B, respectively. In the electron beam method, since the evaporation rate is changed by the remaining amount of evaporation material in the electron beam evaporation sources 5 and 6 (the crucible), it is difficult to control the film thickness of each layer.

Then, in the atmosphere containing the reactive gas in the chamber 8, the components of the hard coat layer A using the arc evaporation sources 5 and 6 and the components of the hard coat layer B using the sputtering evaporation sources 2 and 3, respectively. By evaporation, they are alternately and sequentially laminated on the substrate 1 to form the hard film of the present invention.

For example, when TiN is used as the layer A and SiN is used as the layer B, in the present invention, Ti, which is a component of the layer A, is evaporated to the arc evaporation sources 5 and 6, and Si, which is a component of the layer B, is sputtered. Evaporated). Then, film formation is performed in nitrogen, which is an Ar + reaction gas, which is a sputtering gas, and as described above, the substrate 1 is rotated so that the substrates alternately pass in front of the arc evaporation source and the sputtering evaporation source, thereby alternately transferring TiN and SiN. Furthermore, it can be laminated | stacked on the board | substrate sequentially, and the laminated structure hard film of TiN + SiN of this invention can be formed easily.

Next, embodiment is demonstrated below about the formation method (film formation method) of the hard laminated film of this 2nd invention.

The method for forming the hard laminated film of the present invention, which is recommended, uses a film forming apparatus (see Fig. 5; hereafter referred to as "composite film forming apparatus") provided with at least one arc evaporation source and a sputtering evaporation source each having a magnetic field applying mechanism. In a mixed gas of sputtering gases such as Ar, Ne, and Xe and reactive gases such as nitrogen, methane, acetylene, and oxygen, the component of layer A is the arc evaporation source and the component of layer B while rotating the substrate. Is a method of alternately laminating layers A and B by alternately evaporating to a sputtering evaporation source to effect reactive film formation. The reason for changing the method of the evaporation source to the layers A and B is as described above.

In addition, when forming a layer made of (B, N), (Si, C, N) or (C, N) as the layer B, it is necessary to form a film using a B, BN, B ₄ C, Si, C target or the like. , B and BN are insulative materials and cannot be formed because no discharge occurs in the arc evaporation source. Also, B ₄ C, Si, and C are conductive materials, but they are difficult to form as arc evaporation sources because the discharge is not stable.

On the other hand, when both sputtering evaporation sources are used for the deposition of layers A and B, the sputtering evaporation source operates at low input power, unlike the arc evaporation source, but the deposition rate is slower than that of the arc evaporation source, and the hardness of the formed film is also applied to the arc evaporation source. Falls compared

Therefore, in the present embodiment, the formation of layer A includes Cr or CrX (where X is Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si) as a target in the arc evaporation source. Or two or more elements) and B, BN, B ₄ C, Si, or C targets are used in the sputtering evaporation source to form layer B, while rotating the substrate in a mixed gas of sputtering gas and reactive gas. The layer B is laminated alternately to form a film.

In the case of using the B and BN targets, the sputtering evaporation source uses the RF sputtering method because there is no conductivity. However, when the B ₄ C, Si, and C targets are used, the sputtering evaporation source is the DC and RF both methods. You can use both.

Further, when forming layer A, metal Cr or CrX (where X is one or two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si) In addition, Cr (B, C, O, N) or (Cr, X) (B, C, O, N) is formed by using a target to which at least one element of B, C, O, or N is added. It is also possible.

It is preferable that the partial pressure of the reaction gas in the mixed gas which consists of sputtering gas and reaction gas at the time of film-forming is 0.6 Pa or more, More preferably, it is 1 Pa or more. Although the total pressure of the mixed gas is not particularly limited, it is 1 Pa or more as a standard when considering that the sputtering gas of the reaction gas and almost the same amount is added. However, under high pressure, since the sputtering evaporation source and the arc evaporation source tend to cause abnormal discharges, 5 Pa or less is the standard.

Next, embodiment is demonstrated below about the formation method (film formation method) of the hard laminated film of this 3rd invention.

In the third aspect of the present invention, as shown in FIG. 5 described above, the arc evaporation source and the sputtering evaporation source are formed in a film formation atmosphere containing a reactive gas by using a film deposition apparatus including one or more arc evaporation sources and sputtering evaporation sources in the same vacuum container. Simultaneously operating the components of layer A from the arc evaporation source and the components of layer B from the sputtering evaporation source, while moving the substrate relative to each of the evaporation sources, thereby altering layers A and B on the substrate. The method of lamination is most preferred.

One reason for this is that the film formation speed of the above-mentioned sputtering method is slow. In addition, the layer B mainly has B, Si, C, and Cu as in the said Formula (2-5). For this reason, targets mainly composed of these elements (such as pure Si, B ₄ C, and C) have a problem that the discharge is very unstable in arc discharge. In addition, there is a problem that these targets are broken by the heat load during arc discharge. In addition, Cu targets tend to release a large amount of molten droplets (macroparticles) by evaporation in an arc discharge. Therefore, it is preferable to perform film-forming of layer B by sputtering evaporation source also in the characteristic of these targets for layer B.

In the case where TiAlN is used as the layer A and BCN is used as the layer B, in the present invention, Ti and Al, which are components of the layer A, are evaporated to the arc evaporation sources 5 and 6, and B and C, which are components of the layer B, are sputtered. Evaporate to (2, 3). Then, film formation is carried out in nitrogen, which is an Ar + reaction gas, which is a sputtering gas, and as described above, the substrate 1 is rotated so that the substrates alternately pass in front of the arc evaporation source and the sputtering evaporation source. By alternately and sequentially laminating on the substrate, the hard film of the laminated structure of the present invention can be easily formed.

In the film forming method of the third invention described above, when the arc evaporation source and the sputtering evaporation source are operated at the same time to form a hard film containing nitrogen, the film forming atmosphere is formed by a reactive gas such as nitrogen, methane, acetylene (reaction). Gas) and an inert gas for sputtering such as Ar (argon), Ne (neon), Xe (xenon), and the like.

And it is preferable to make the partial pressure of the mixed reactive gas into 0.5 Pa or more. When the film is formed under a condition where the partial pressure of the reactive gases to be mixed is less than 0.5 Pa, addition of nitrogen or the like into the hard film is insufficient, and large particles in the hard film also increase. For this reason, a dense film becomes difficult to complete.

On the other hand, in order to sufficiently add nitrogen into the hard film, to suppress the generation of large particles in the hard film, and to form a film having a dense and excellent surface property, the partial pressure of the reactive gas mixed in the sputtering gas is determined as described above. Similarly, it is preferable to set it as 0.5 Pa or more.

Next, embodiment is demonstrated below about the formation method (film formation method) of the hard laminated film of this 4th invention.

In the fourth aspect of the present invention, as shown in FIG. 5 described above, the arc evaporation source and the sputtering evaporation source are formed in a film formation atmosphere containing a reactive gas by using a film formation apparatus including one or more arc evaporation sources and sputtering evaporation sources in the same vacuum vessel. Simultaneously operating the components of layer A from the arc evaporation source and the components of layer B from the sputtering evaporation source, while moving the substrate relative to each of the evaporation sources, thereby altering layers A and B on the substrate. The method of lamination is most preferred.

One reason for this is that the deposition rate of the sputtering method is slow. When each of the layers A and B is formed on the substrate using only the plurality of sputtering evaporation sources described above, the thickness of each of the layers A and B is determined by the operation time of each sputtering evaporation source or the deposition time using the shutter on the front surface. It is possible by controlling. However, in the sputtering method, since the film formation rate is slow, it takes time to form the layer A which requires twice the film thickness of the layer B and is not efficient.

In addition, the layer B contains W, Mo, V, and N, as in the composition of Formula 7, wherein the target mainly containing these elements is a high melting point, and in arc discharge, the discharge may become unstable due to the increase in voltage. have. Also from this point of view, it is preferable to perform the film formation of the layer B by the sputtering evaporation source and to perform the film formation of the layer A by the arc evaporation source.

In the case where TiAlN is used as the layer A and WN is used as the layer B, in the present invention, Ti and Al, which are components of the layer A, are evaporated to the arc evaporation sources 5 and 6, and W, which is a component of the layer B, is sputtered and evaporated (2). , 3). Then, film formation is performed in nitrogen, which is an Ar + reaction gas, which is a sputtering gas, and as described above, the substrate 1 is rotated to alternately pass TiAlN and WN by alternately passing the arc evaporation source and the sputtering evaporation source. In addition, by sequentially laminating on the substrate, it is possible to easily form a hard film of the laminated structure of the present invention.

(Reaction gas partial pressure)

In the film forming method of the fourth invention described above, when the arc evaporation source and the sputtering evaporation source are operated at the same time to form a hard film containing nitrogen, the film forming atmosphere is formed by a reactive gas such as nitrogen, methane, acetylene (reaction). Gas) and an inert gas for sputtering such as Ar (argon), Ne (neon), Xe (xenon), and the like.

And it is preferable to make the partial pressure of the mixed reactive gas into 0.5 Pa or more. In the case where the partial pressure of the reactive gas to be mixed is formed under a low condition of less than 0.5 Pa, addition of nitrogen or the like into the hard film becomes insufficient, and large particles in the hard film also increase. For this reason, a dense film cannot be formed.

On the other hand, in order to sufficiently add nitrogen into the hard film, to suppress the generation of large particles in the hard film, and to form a film having a high surface property with a high density, the partial pressure of the reactive gas mixed in the sputtering gas is as described above. It is preferable to set it as 0.5 Pa or more.

(Example)

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not restrict | limited by the following example of course, Of course, it implements by changing suitably in the range which may be suitable for the meaning of the previous and the later. Possible, these are all included in the technical scope of the present invention. First, the embodiment of the first invention will be described.

Example 1-1

The influence of the crystal structure of layer B was investigated below. That is, the presence or absence of the refinement | miniaturization effect of a crystal grain when selecting the material whose crystal structure is a cubic rock salt-type structure as layer A, and the material whose crystal structure is the same cubic rock salt-type structure or the material which has a different crystal structure as layer B is selected. It was confirmed.

Specifically, the film which has a laminated structure shown in Table 1 was formed using the sputtering film-forming apparatus which has the binary sputtering evaporation sources 2 and 3 shown in the said FIG. As the board | substrate 1, the cemented carbide (hardened surface was polished) for hardness measurement was used. After introducing this substrate into the apparatus of FIG. 3, while heating the substrate temperature to about 400 to 500 ° C, the substrate was evacuated to a vacuum of 3 x 10 &lt; ^-3 &gt; Pa or less, and cleaned with Ar ions (pressure 0.6 Pa, substrate voltage 500 V). , Treatment time 5 minutes), and subsequently, film formation was performed.

At the time of film formation, in the case of forming a metal film, in a pure Ar atmosphere, in the case of forming a nitride, in a mixed gas of Ar and nitrogen (mixing ratio 65:35), in the case of carbonitride, Ar, nitrogen, and methane are mixed. In the gas (mixing ratio 65: 30: 5) atmosphere, the total pressure was constant at 0.6 Pa to form a film.

The thickness of layer A and layer B was adjusted to the time to operate each sputtering evaporation source (2, 3), but the thickness of layer A was constant at 50 nm, the thickness of layer B was 10 nm, and the repetition of layer A and layer B was repeated. A total of 50 layers (lamination units) were laminated to form a film having a thickness of about 3000 nm. The TEM observation of the cross section of the film was carried out 45000 times about the test material after film-forming, and the presence or absence of the refinement | miniaturization effect of a crystal grain as shown in FIG. 1 was confirmed. And when there existed this effect, (circle) and when there was no effect, it evaluated by x. These results are shown in Table 1.

As shown in Table 1, in the comparative examples of Nos. 1 to 4, although a material having a crystal structure of cubic rock salt structure was selected as layer A, a material having a crystal structure of cubic rock salt structure was similarly selected as layer B. have. For this reason, the division of grain growth does not occur between layer A and layer B, crystal grains are growing continuously, and it was confirmed that there is no refinement | miniaturization effect of a crystal grain.

On the other hand, in the case of the invention examples of Nos. 5 to 13, when a material having a crystal structure different from that of the layer A was selected as the layer B, as shown in FIG. 1, the crystals are not continuously grown between the layers A and B. As a result, the crystal grains of the layer A were refined to the thickness of the layer A (50 nm). In addition, although AlN used for the layer B of the comparative example 4 is a material with a stable hexagonal B4 type structure, when lamination | stacking with the material of the layer A of the rock salt type structure like this Example, in the formed film, the AlN layer will rock salt. It became a mold structure, and the effect of grain refinement of layer A was not seen.

From the above results, when forming a laminated structure hard film composed of the layer A of the cubic rock salt structure, there is no effect of miniaturization of crystal grains unless a material having a crystal structure different from that of the layer A of the cubic rock salt structure is selected as the layer B. This was confirmed.

Example 1-2

Based on the result of this Example 1-1, the influence of the crystal structure of layer B was investigated in more detail. That is, as a layer A, a hard coating material having a rock salt cubic structure such as TiAlN, CrN, TiN, etc. is selected, and as a layer B, a material having a crystal structure other than a rock salt cubic structure such as Cu, Co, SiN, BN, CrN, MoN When the material which has rock salt cubic crystal structures, such as WN, TaN, and AlN, was selected, or when layer B is not provided, the presence or absence of the refinement | miniaturization effect of a crystal grain, and the film hardness were confirmed.

Specifically, the film which has a laminated structure shown in Table 2 using the sputtering film-forming apparatus which has the binary sputtering evaporation source 2 and 3 shown in the said FIG. 3, and the composite film-forming apparatus of the arc and sputtering shown in the said FIG. Formed. As a board | substrate, the cemented carbide (mirror polishing) for hardness measurement similar to Example 1-1 was used. After both devices introduced the substrate into the device, the substrate temperature was heated to about 400 to 500 ° C., and then evacuated to a vacuum of 3 × 10 ⁻³ Pa or less, followed by cleaning with Ar ions (pressure 0.6 Pa, substrate voltage 500 V, After 5 minutes of treatment time), each film formation was performed.

In the case of the sputtering film forming apparatus shown in Fig. 3, in the case of forming nitride at the time of film formation, in the mixed gas of Ar and nitrogen (mixing ratio 65:35), in the case of carbonitride, the mixed gas of Ar, nitrogen and methane (mixing ratio) 65: 30: 5) In the atmosphere, the film was formed at a total pressure of 0.6 Pa, and the thicknesses of the layers A and B were adjusted by the time for operating each evaporation source.

In the composite film forming apparatus shown in Fig. 5, in the case of forming a nitride at the time of film formation, in a mixed gas of Ar and nitrogen (mixing ratio 50:50), in the case of carbonitride, a mixed gas of Ar, nitrogen, and methane (mixing ratio) 50: 45: 5) In the atmosphere, the film was formed at a total pressure of 2.66 Pa. The thickness of the layer A and the layer B was determined by the power ratio put into each evaporation source, and the ratio of the thickness of the layer A + layer B was determined by the rotation period of the substrate. The film thickness was made constant at almost 3 μm. In addition, layer A was formed in the arc evaporation source, and layer B was formed in the sputtering evaporation source.

Evaluation of the hardness of the mechanical properties of the formed film was measured by a MicroVickers hardness tester (load 25 gf). In addition, the crystal structure of layer A and layer B is interpreted by TEM observation of 45000 times the cross section of a film, and the film thickness and the size of crystal grains of layer A and layer B are determined from the cross-sectional TEM image, and the effect of grain refinement of layer A The presence or absence of was evaluated in the same manner as in Example 1-1. These evaluation results are shown in Table 2.

As can be seen from Table 2, as inventive examples 20, 21, 24 to 27, 29, a hard coat material having a rock salt cubic structure such as TiAlN, CrN, TiN, etc. was selected as the layer A, and Cu, Co was used as the layer B. Only when a material having a crystal structure other than rock salt cubic structures such as SiN and BN is selected, the micronized effect of the grains and a significant increase in the film hardness are observed.

On the other hand, when the layer B is not provided as in Comparative Examples 14 to 19, when the material having the rock salt cubic structure is selected as the layer B as in Comparative Examples 22, 23 and 28, there is no effect of miniaturization of crystal grains and the film hardness. Relatively low.

Example 1-3

Next, the influence of the thickness of the layer B made of a material having a crystal structure other than the rock salt cubic crystal structure on the micronized effect of the grains on the layer A was investigated.

As a film-forming apparatus, the test material was produced on the same conditions using the same sputtering apparatus and composite film-forming apparatus as Example 1-2. As the layer A, (Ti _0.5 Al _0.5 ) N, CrN and TiN having high hardness were selected as representative of the material having a rock salt cubic structure, and SiN, BN and Cu were selected as the layer B. Si, B ₄ C and Cu targets were used for the formation of the layers of SiN, BN and Cu, respectively.

And the thickness of layer A was made constant at 30 nm, the thickness of layer B was changed to the range of 0.2-100 nm, and the influence of the thickness of layer B on the refinement | miniaturization effect of a crystal grain was investigated. About the test material after film-forming, the presence or absence of refinement | miniaturization of the crystal grain by hardness measurement and sectional TEM was confirmed similarly to Example 1-2. These results are shown in Table 3.

In the comparison in each group of numbers 30-36, 37-43, 44-50 which conditions other than the thickness of layer B in Table 3 are the same, the thickness of layer B also in any case of each group In the case of the examples of Nos. 30, 37, and 44, where is 0.2 nm smaller than 0.5 nm, refinement of grains did not occur. For this reason, it is preferable that the thickness of the layer B has a thickness of about 0.5 nm or more that exceeds this 0.2 nm at least.

In addition, in Table 3, on the contrary, in the case of No. 35, 36, or 42, 43, or 49, 50, the thickness of layer B relative to layer A is relatively greater than 1/2 of the layer A thickness. As the characteristic of the entire coating, the characteristic of the layer B becomes dominant. As a result, in comparison with 31 to 34, or 38 to 41, or 45 to 48, which is an example in which the thickness of the layer B with respect to the layer A in each group is relatively small, no significant increase in hardness is seen. Therefore, it can be seen that the thickness of the layer B is preferably 1/2 or less of the thickness of the layer A.

Example 1-4

Next, the influence of the thickness of the layer A on the grain refinement and hardness of the hard film was investigated.

As the film-forming apparatus, the composite film-forming apparatus of FIG. 5 used in Example 1-2 was used and (Ti _0.5 Al _0.5 ) N as layer A and SiN as layer B were formed on the same conditions as Example 1-2. The test material which made the thickness of the layer B constant at 2 nm, and changed the thickness of the layer A in the range of 1-300 nm was created. About the test material, the refinement | miniaturization of the crystal grain by the hardness measurement and the cross-sectional TEM was confirmed similarly to Example 1-2. The evaluation results thereof are shown in Table 4.

From Table 4, in the case of the example of No. 51 where the thickness of the layer A was thin at 1 nm with respect to the thickness of the layer B of 2 nm, the characteristics of the layer B became dominant as the entire film, and the grains were refined, but other numbers 52 to 55 and the like were obtained. Compared with the example, hardness fell in reverse. On the other hand, in the case of the example of No. 53 where the thickness of the layer A exceeds 200 nm, there is no grain refinement effect, and since the size of a crystal grain approaches a conventional product, hardness becomes substantially equivalent to a conventional product. Therefore, the thickness of the layer A is preferably in the range of 2 to 200 nm.

Example 1-5

Next, the oxidation resistance improvement effect according to the kind of material selected as layer B was investigated by the oxidation start temperature of a hard film.

As the film-forming apparatus, the composite film-forming apparatus of FIG. 5 used also in the said Example 1-2 was used, (Ti _0.5 Al _0.5 ) N as layer A, and SiN, BN, MoN, and Ti as layer B was platinum foil (0.1 mm thickness). Formed). The film thickness of layer A and layer B was made constant at 30 and 2 nm, laminated | stacked about 90 layers in total by the unit of layer A + layer B, and formed the film.

Oxidation increase was measured in the temperature range up to 1000 degreeC with respect to the formed film, and oxidation resistance was investigated. Thermal balance was used for irradiation of oxidation resistance, and it heated to 1000 degreeC in the drying air at the temperature increase rate of 4 degree-C / min, and the oxidation start temperature was determined from the weight increase by oxidation. These evaluation results are shown in Table 5.

As can be seen from Table 5, in the case of Inventive Examples 58 and 59 in which SiN and BN were selected as the layer B, the oxidation of the comparative example 57 corresponding to the conventional material without the layer B or the comparative example 60 of the rock salt crystal structure For the onset temperature of 850 ° C, the oxidation onset temperature increased to 900 ° C. Therefore, when SiN and BN were selected as the layer B in the film structure of the present invention, it can be seen that SiN and BN not only increase the hardness but also improve the oxidation resistance. In addition, inventive example 61 in which Ti was selected as the layer B has a grain refinement effect of the layer A, but the oxidation start temperature is relatively low.

Example 1-6

Next, as a difference in the film forming conditions, the effects of the case where the magnetic lines of the arc evaporation source and the sputtering evaporation source were connected, and the magnetic lines of the respective evaporation sources were not connected, were formed. The film formation was carried out in the same manner as in the previous examples, with a layer of (Ti _0.5 Al _0.5 ) N as a layer A, 30 nm as CrN, SiN, BN as a layer B as 3 nm, and a total of about 90 layers in a layer A + layer B. Formed.

Although the complex film-forming apparatus of FIG. 5 was used for this film-forming, the arrangement which connected the magnetic lines of the arc evaporation source and the sputtering evaporation source of FIG. 5 for comparison, and the arrangement which does not connect the magnetic lines of each of these evaporation sources of FIG. It formed into a film and the characteristic was compared and investigated. These evaluation results are shown in Table 6. In addition, film-forming conditions with the apparatus of FIG. 5 and FIG. 6 were made into the same conditions as the film-forming conditions of the apparatus of FIG. 5 of Example 1-2.

As can be seen from Table 6, the examples of numbers 62 and 64 in the case where magnetic lines are connected to each other (in Fig. 5) are compared with the examples in numbers 63 and 65 in the case where the lines are not connected to each other (in Fig. 6). 62 and 63, 64 and 65), the properties are almost the same in terms of oxidation resistance, but the hardness is high. From these results, as shown in FIG. 5, it can be seen that a film having a higher hardness can be formed by increasing the ion density in the film forming side connecting the magnetic lines of force.

Next, the Example of this 2nd invention is described.

Example 2-1

A film having a laminated structure shown in Table 7 was formed by using a sputtering film deposition apparatus having two sputtering evaporation sources shown in FIG. 3 or a composite film formation apparatus having two sputtering evaporation sources and two arc evaporation sources shown in FIG. 5. It was.

As a substrate, a cemented carbide (mirror polishing) for hardness measurement was used. Even when using any of the sputtering film forming apparatuses and the composite film forming apparatuses, the substrate is charged into the apparatus and heated, and the substrate temperature is maintained at about 400 to 500 ° C. until the vacuum state is 3 × 10 ⁻³ Pa or less. After exhausting and cleaning with Ar ions (pressure 0.6 Pa, substrate voltage 500V, processing time 5 minutes), film formation was performed.

In the case of using a sputtering film forming apparatus, in the case of forming a metal film during film formation, in the case of forming a carbon nitride in a pure Ar atmosphere in the case of forming a nitride, in a mixed gas (volume mixing ratio 65:35) atmosphere of Ar and nitrogen In an atmosphere of a mixed gas of Ar, nitrogen, and methane (volume mixing ratio 65: 30: 5), the film is formed under the condition of a total pressure of 0.6 Pa, and the thicknesses of the layers A and B are adjusted by changing the time for operating each evaporation source. It was. Metal Cr and B were used for the target.

In the case of using a composite film forming apparatus, a mixed gas of Ar and nitrogen (volume mixing ratio 50:50), a carbon mixed gas of Ar, nitrogen and methane (volume mixing ratio 50: 45: 5), and a total pressure of 2.66 Pa It formed into a film underneath, and the film thickness ratio of layer A and layer B was adjusted by the ratio of the input electric power to each evaporation source, and the thickness of layer A and layer B was adjusted by the rotation speed of a board | substrate.

The total thickness of the formed film was made constant at nearly 3 micrometers. In addition, layer A was formed at the arc evaporation source and layer B was formed at the sputtering evaporation source. As a target, metal Cr was used for the arc evaporation source and conductive B ₄ C was used for the sputtering evaporation source.

First, using the sputtering film forming apparatus and the composite film forming apparatus, respectively, the layer A is made of CrN, the layer B is made of B _0.45 C _0.1 N _0.45 , the thickness of the layer A is constant at 30 nm, and the thickness of the layer B is 0.2 The film formation was carried out with various changes in the range of from 50 nm (test numbers 2 to 7, 9 to 14). For comparison, film formation of only layer A was also performed as a conventional method (test numbers 1 and 8).

Moreover, using only a composite film-forming device, by changing the layer A in the proportion of Cr ₂ N, the film formation was performed in the same conditions as described above (test Nos. 15 to 21).

As a result of performing cross-sectional TEM observation about the test material after film-forming, the refinement | miniaturization effect of the crystal grain as shown in FIG. 7 was confirmed. When the magnitude | size of a crystal grain is about the same as the conventional film which does not have a laminated structure, it evaluated as (x), when smaller than a conventional film.

In addition, the thickness of each layer of A and B after film-forming was observed and measured by 2 fields of view at 50 to 1.5 million times magnification.

The ratio of the metal element in each film, and elements, such as N, C, O, was calculated and calculated | required from the composition profile of the depth direction taken while sputtering with Ar ion from the surface by Auger electron spectroscopy.

In addition, the hardness of the obtained film was measured by the micro-Vickers hardness tester (load 25 gf [≒ 0.245N], holding time 15 second).

In addition, the abrasion resistance of the film and the aggression to the counterpart were evaluated using a ball-on-plate type reciprocating sliding motion wear friction tester. Using a bearing steel (SUJ2, HRC60) with a diameter of 9.53 mm as the counterpart (ball), a sliding test was carried out in a dry environment at a sliding speed of 0.1 m / s, a load of 2 N, and a sliding distance of 250 m. The friction coefficient in and the wear rate of each of the ball and the film were measured to evaluate the properties of the film.

Moreover, the X-ray diffraction measurement of (theta) -2 (theta) using CuK (alpha) ray was performed, and the half value width of the (111) and (200) plane was measured.

The results of the test are shown in Table 7. In addition, the number of lamination | stacking shown in Table 7 counted the state which laminated | stacked layer A and layer B one by one as one lamination | stacking (same as Tables 8-10).

The following are clear from these test results. That is, when the thickness of the layer B is less than 0.5 nm, the effect of grain refinement cannot be obtained, and the degree of increase in the hardness of the film is small (see Test Nos. 1, 2, 8, 9, 15, and 16). On the other hand, when the thickness of the layer B is too large, the grain size becomes finer, but since the ratio of the thickness of the low hardness layer B to the thickness of the high hardness layer A becomes excessive, the hardness of the entire coating film tends to decrease. (See Test Nos. 7, 14, 21). Therefore, the film thickness of layer B is preferably 0.5 times or less of the film thickness of layer A (see Test Nos. 3 to 6, 10 to 13, 17 to 20).

The wear coefficient of the film also tends to be almost the same as the hardness, but the wear rate of the film is almost unchanged when the thickness of the layer B is smaller than the thickness of the layer A (test numbers 1 to 6, 8 to 13, 15 to 20), which tends to increase rapidly when the layer A is larger than the thickness of the layer A, suggesting a decrease in wear resistance (see Test Nos. 7, 14 and 21).

In addition, in addition to satisfying the formulas (1), (6) and (7), the layer A is formed of CrN having a rock salt cubic structure, and at least one of the half widths of the diffraction lines on the (111) plane and the (200) plane is 0.3 ° or more. It can be seen that a coating having high hardness and excellent wear resistance can be obtained (see Test Nos. 3 to 6 and 10 to 13).

Example 2-2

In the present Example, although the layer A was set as CrN and the layer B was set to B _0.45 C _0.1 N _0.45 similarly to Example 2-1 using the same composite film forming apparatus as used in Example 2-1, the layer The film was formed by varying the thickness of B in a range of 1 to 300 nm while keeping the thickness of B constant to 2 nm. In addition, other test conditions are the same as Example 2-1.

The test results are shown in Table 8. The following are clear from these test results.

If the thickness of the layer A is smaller than the thickness of the layer B, the degree of increase in hardness of the film is small because the properties of the relatively low hardness layer B become dominant (see Test No. 31). On the other hand, when the thickness of the layer A exceeds 300 nm, the effect of the division and refinement of the crystal grains by the layer B becomes small, and rather, the hardness of the film tends to decrease (see Test No. 36). Therefore, while the film thickness of layer A is 200 nm or less, the film thickness of layer B is preferably 0.5 times or less of the film thickness of layer A.

Example 2-3

In this embodiment, the thickness of layer A is 30 nm and the thickness of layer B is set to 2 nm, respectively, using the same sputtering film forming apparatus or the composite film forming apparatus as used in Example 2-1, respectively. The film formation was performed by varying the composition of. In the case of containing C or O in the layer A, methane or oxygen gas was added to the reaction gas, and in the case of containing B, a Cr-B alloy target containing B in the target was used. In addition, other test conditions are the same as Example 2-1.

The test results are shown in Table 9 and Table 10. From these test results, it can be seen that the coating having excellent wear resistance at high hardness can be obtained by setting the layers A and B to the compositions satisfying the general formulas (1) and (2), respectively.

In the case where the layer B has a SiCN-based composition, the friction coefficient of the film is slightly higher and the wear rate of the ball is slightly higher than that of the BCN-based composition, but the hardness of the film is equivalent to slightly higher. It has been found that the film is suitable for cutting tools, etc., which do not have to be considered and the attack on the counterpart is not considered.

This means that when the layer B is made of a composition other than the SiCN-based composition in the composition stipulated in the present invention, it is possible to obtain an effect of reducing the aggression to the counterpart material than the conventional coating.

Next, the Example of this 3rd invention is described.

Example 3-1

The hard laminated film and the single-layer hard film of various conditions were formed into a film, the film hardness was investigated, the effect of laminating layers A and B in this invention alternately, and the effect of each thickness with layers A and B was evaluated.

At this time, in the case of the arc film forming method, the film was formed using only the arc evaporation source of the film forming apparatus having the arc and the sputtering evaporation source shown in FIG. In the case of the sputtering film forming method, the film was formed by a film forming apparatus having only the binary sputtering evaporation source shown in FIG. 3. In the case of the arc + sputtering film forming method, each film having the composition shown in Table 11 was formed by using the film forming apparatus having the arc and the sputtering evaporation source shown in FIG. 5.

All of these film-forming apparatuses are common, and after evacuating a board | substrate to an apparatus, it heats with a vacuum below 3x10 <^-3> Pa, heating a board | substrate temperature to about 400-500 degreeC, and cleaning with Ar ion (pressure 0.6 Pa, Substrate voltage 500V, processing time 5 minutes), and it formed into a film.

In addition, all these film-forming apparatuses were common, The temperature at the time of film-forming was all 400-500 degreeC. As a base material, the mirror-polished cemented carbide was used. To form a coating film of the layer A using a target containing a metal component of the layer A joseongjung shown in Table 11 and, when forming the layer B ₄ C was used as B, C, Si, for each target of Cu.

At this time, the laminated film thickness (film thickness) was made constant at almost 3 micrometers (3000 nm) in each case. In addition, the thickness of layer A was 2-250 nm, and the thickness of layer B was each changed in the range of 0.2-30 nm.

In the sputtering film forming apparatus of FIG. 3, in forming a metal film during film formation, in a pure Ar atmosphere, in the case of forming a nitride, a mixed gas of Ar and nitrogen (mixing ratio 65:35), and in the case of carbonitride The film was formed with a mixed gas of nitrogen and methane (mixing ratio 65: 30: 5) and a total pressure of 0.6 Pa, and the thicknesses of the layers A and B were adjusted by the time for operating each evaporation source.

In the composite film forming apparatus of FIG. 5, a mixed gas of Ar and nitrogen (mixed 50:50), a mixed gas of Ar, nitrogen and methane (mixed ratio 50: 45: 5) in the case of carbonitride, and a total pressure of 2.66 Pa It formed into a film. In addition, layer A was formed at the arc evaporation source and layer B was formed at the sputtering evaporation source. In addition, the thickness of layer A and layer B was determined by the electric power ratio put into each evaporation source, and the laminated film thickness of the sum total of layer A + layer B was determined by the rotation period of a board | substrate.

About each of these formed films, the Vickers hardness of the film was evaluated by the micro-Vickers hardness tester (measurement load 25gf: Hv0.25).

In addition, the cross-sectional TEM photographs confirmed the lamination cycle and the thicknesses of the layers A and B. The composition was analyzed by the Auger electron spectroscopy in the depth direction of each film. These results are shown in Table 11.

As shown in Table 11, the comparative example of the numbers 1-5 is the case of the single | mono layer of only the layer A which does not have layer B. FIG. On the other hand, the layer A is the same composition, such as Comparative Example 1, Inventive Examples 7-8, Comparative Example 3, Inventive Examples 12-14, Comparative Example 4, Inventive Examples 17-19, Comparative Example 5, Inventive Examples 22-24, etc. In comparison of phosphorus, each of these invention examples ensures high hardness compared with each comparative example. Therefore, first, the effect of alternately laminating layers A and B in the present invention is supported.

Next, numbers 6 to 15 show the effect of the film thickness of layer B. In the comparison in each group of Nos. 6 to 10 and 11 to 15, in which layers A and B of the same composition in the scope of the invention were provided, respectively, Comparative Examples 6 and 11 were 0.5, in which the thickness of layer B was the lower limit. less than nm. In Comparative Examples 10 and 15, the thickness of layer A is less than twice the thickness of layer B. As a result, these comparative examples were compared with the same group of Inventive Examples 7-9 and Inventive Examples 12-14 whose relationship between the thickness of layer A, layer B, and the thickness of layer A and layer B satisfy | fills the specification of this invention. Hardness is relatively low.

Nos. 16 to 25 show the effect of the film thickness of layer A. In comparison in each group of No. 16-20 and 21-25 which provided the layer A and the layer B of the same composition within the scope of the present invention, Comparative Examples 16 and 21 have the thickness of layer A being layer B Is less than twice the thickness of. In Comparative Examples 20 and 25, the thickness of the layer A exceeded the upper limit of 200 nm. As a result, these comparative examples were much harder than the same group of Inventive Examples 17 to 19 and Inventive Examples 22 to 24, in which the relationship between the thickness of the layer A and the thickness of the layer A and the layer B satisfies the requirements of the present invention. low.

Therefore, the meaning of the thickness of the layer A, the layer B, the relationship between the thickness of the layer A, and the layer B, and the more preferable definition in this invention are supported.

Example 3-2

Next, the layer A of various compositions was formed into a film, the film hardness was investigated, and the influence (effect) on the film hardness of the composition of the layer A in this invention was evaluated.

Under the same film formation conditions as in Example 3-1, films having various compositions shown in Table 12 were formed. About the formed film, the film Vickers hardness similar to Example 3-1 was evaluated with the micro Vickers hardness tester (measurement load 25gf). In addition, the cross-sectional TEM photograph confirmed the lamination cycle and the thickness of the layers A and B. In addition, the composition was analyzed in depth direction of a film by Auger electron spectroscopy. These results are shown in Table 12.

As shown in Table 12, the comparative example of the numbers 1-6 is the case of the single | mono layer of only layer A which is not equipped with layer B. FIG. On the contrary, in the comparison of compositions having the same layer A, such as Comparative Example 1 and Inventive Example 12, Comparative Example 2 and Inventive Example 17, Comparative Example 3 and Inventive Example 13, Comparative Example 4 and Inventive Example 29, Honor secures high hardness compared with each comparative example. In addition, in the comparison between Comparative Examples 6 and 7 in which the layer A was TiN while comparing the same comparative examples, the comparative example 6 of the single layer only of the layer A without the layer B alternates between the layer A and the layer B. The hardness is lower than that of Comparative Example 7, which was laminated with. Therefore, also from the results of Table 12, the effect of alternately laminating layer A and layer B in the present invention is supported.

Layer A in the present invention consists of a composition of formula (1) as described above.

Formula 1

(Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

[In the above, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and M is one or more of 4A, 5A, 6A, and Si. Metal element selected]

Here, in Table 12, the example of the same component system is compared. First, in the (TiAl) N system, the Al content is too low or too high out of the prescribed range of 0.4 ≦ x ≦ 0.8. The hardness is lower than that.

In the (TiAlCr) N system, in Comparative Example 16, where the content of Al is out of the prescribed range of 0.4≤x≤0.8 and is too low, the content of Cr may be too high outside of the prescribed range of 0≤y≤0.6, The content x of 0.45 to 0.65 is in the above prescribed range of 0.4 to 0.8, and the hardness is lower than the invention examples 13 to 15 which are also within the prescribed range of 0.55 to 0.75.

Therefore, from these results, the meaning of the definition of content x of Al of layer A in this invention, or a more preferable definition is supported.

In the (TiM) (BN) system, the content of B is too high out of the prescribed range of 0 ≦ a ≦ 0.15. In Comparative Example 25, the content of B is within the prescribed range of 0.15 or less, and more preferably 0.1 or less Hardness is low compared with invention examples 23 and 24 which are also in a range.

Therefore, these results support the meaning of the provision of content a of B of the layer A or more preferable provision of the present invention.

In the (TiAlCr) (CN) system, the content of C is too high out of the prescribed range of 0≤b≤0.3, and the comparative example 28 has a content of C within 0.3 or less, more preferably within 0.1 or less Hardness is low compared with invention examples 26 and 27 which are also.

Therefore, from these results, the meaning of the definition of content b of C of the layer A in this invention, or a more preferable regulation is supported.

In the (TiAlV) (ON) system, Comparative Example 30 in which the O content is too high out of the prescribed range of 0 ≦ c ≦ 0.1 is lower in hardness than Inventive Example 29 in which the O content is within the specified range of 0.1 or less.

Therefore, these results support the significance of the definition of the O content of the layer A in the present invention.

In addition, invention examples 13-15, 17-22 of Table 12 contain Cr, Si, Zr, Nb, Ta, V as addition element M. As shown in FIG. Among these elements M, the hardness of the example containing Cr, Si, V, etc. is especially high. Therefore, the effect of improving the hardness of these elements M is supported.

Example 3-3

Next, the layer B of various compositions was formed into a film and the film hardness was investigated, and the influence (effect) on the film hardness of the composition of the layer A in this invention was evaluated.

Under the same film formation conditions as in Example 3-1, a film having various compositions shown in Table 13 was formed. About the formed film, the Vickers hardness of the film was evaluated similarly to Example 3-1 and 3-2. In addition, the cross-sectional TEM photograph confirmed the lamination cycle and the thickness of the layers A and B. In addition, the composition was analyzed in depth direction of a film by Auger electron spectroscopy. These results are shown in Tables 13 and 14 (continued in Table 13).

In addition, in the present Example, evaluation of the sliding motion characteristic of each film was evaluated by the ball-on-plate type reciprocating sliding motion wear friction tester. Evaluation conditions were performed by testing the counterpart material (ball) in a dry environment at a bearing steel (SUJ2, HRC60) having a diameter of 9.53 mm, room temperature, a sliding speed of 0.1 m / s, a load of 2 N, and a sliding distance of 250 m in a dry environment. Friction coefficient ((mu)) was evaluated.

In the present Example, the oxidation resistance of each film was evaluated from the oxidation start temperature. That is, the film sample formed about 3 micrometers in platinum foil was heated at the speed | rate of 4 degree-C / min in dry air from room temperature to 1100 degreeC using thermobalance, and the oxidation start temperature was determined from this oxidation weight increase curve. These results are also shown in Tables 13 and 14.

As shown in Table 13, 14, the comparative example of the numbers 1-6 is a case of the single | mono layer of only layer A which is not equipped with layer B. FIG. On the contrary, in comparison with Comparative Example 1, Inventive Examples 7 to 10 or Comparative Example 11, in comparison with Comparative Example 3 and Inventive Examples 12, 13, 16 to 19, in comparison with Comparative Example 4 and Inventive Examples 25 to 28 and the like. Thus, each of these inventive examples ensures high hardness as compared with each comparative example. Therefore, also from the results of these Tables 3 and 4, the effect of alternately laminating layers A and B in the present invention is supported.

In the present invention, layer B is selected from the compounds represented by the following four compositional formulas as described above.

Formula 2

B _1-xy C _x N _y

[Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, B / N ≦ 1.5]

Formula 3

Si _1-xy C _x N _y

[Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, 0.5 ≦ Si / N ≦ 2.0]

Formula 4

C _1-x N _x

[Wherein, x represents an atomic ratio and 0 ≦ x ≦ 0.6]

Formula 5

Cu _1-y (C _x N _1-x ) _y

[Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.5]

Consists of a composition selected from any one of

Here, in Tables 13 and 14, examples of component systems having the same layer B are compared. First, in the B _1-xy C _x N _y system, Comparative Example 11 in which the content x of C is too high out of the prescribed range of 0 ≦ x ≦ 0.25 is inventive examples 7 to 10 in which the content of C is within the specified range. The hardness is lower than that. In addition, Comparative Examples 14 and 15, which are too high out of the specification of B / N of 1.5 or less, have lower hardness and higher friction coefficients than Comparative Examples 12 and 13 within the specified range. It can be seen that both the hardness and the friction coefficient of the film are increased under the B / N specification of 1.5 or less.

In the Si _1-xy C _x N _y system, Comparative Example 20 in which the content x of C is too high out of the prescribed range of 0 ≦ x ≦ 0.25 is compared with Inventive Examples 16 to 19, wherein the content x of C is in the prescribed range. Low hardness and oxidation resistance When content x of C is 0.25 or less, it turns out that both the hardness and oxidation resistance of a film become favorable. In addition, Comparative Example 24, which is too low from the 0.5 to 2.0 specification of Si / N, has a lower hardness than Inventive Examples 21 to 23 within the specification range.

In the Cu _1-y (C _x N _1-x ) _y system, in Comparative Example 29, where the coefficient y of the ratio of CN to Cu is too high out of the prescribed range of 0 ≦ y ≦ 0.5, the content x of N is defined The hardness is lower than that of Inventive Examples 25 to 28 in the range. From this result, it turns out that hardness becomes high in the range whose coefficient y of the ratio of CN with respect to Cu is 0-0.5, and hardness becomes high when C content x is 0 <= x <= 0.1.

In the C _1-x N _x system, Comparative Example 34, in which the content x of N is too high out of the prescribed range of 0 ≦ x ≦ 0.6, has a hardness higher than that of Inventive Examples 30 to 33, wherein the content x of N is within the specified range. Low, friction coefficient increased. Therefore, it turns out that hardness x becomes high and a friction coefficient falls within content x of N in a prescribed range.

In addition, in the examples of Tables 3 and 4, the oxidation resistance also slightly increases in the BCN system in which the friction coefficient is reduced by lamination with the BCN-based and C-based layers, which are the layer B. In the SiCN system, the friction coefficient hardly changes, but oxidation resistance is significantly increased. In the CuCN system, the hardness increases and the oxidation resistance also increases slightly.

Therefore, the significance of each composition regulation of the layer B in this invention is supported from these results.

Next, the Example of this 4th invention is described.

Example 4-1

The hard laminated film and the single-layer hard film of various conditions were formed into a film, the film hardness was investigated, and the effect of layering A and B alternately in this invention, and the effect of each thickness with layer A and B was evaluated.

At this time, in the case of the arc film forming method, the film was formed using only the arc evaporation source of the film forming apparatus having the arc and the sputtering evaporation source shown in FIG. In the case of the sputtering film-forming method, it formed into a film-forming apparatus which has only the binary sputtering evaporation source shown in FIG. And in the case of the arc + sputtering film forming method, each film of the composition shown in Table 15 was formed using the film-forming apparatus which has the arc and sputtering evaporation source shown in FIG.

All of these film-forming apparatuses are common, and after evacuating a board | substrate to an apparatus, it heats with a vacuum below 3x10 <^-3> Pa, heating a board | substrate temperature to about 400-500 degreeC, and cleaning with Ar ion (pressure 0.6 Pa, Substrate voltage 500V, processing time 5 minutes), and it formed into a film.

In addition, all these film-forming apparatuses made the temperature at the time of film-forming in common between 400-500 degreeC. As a base material, the mirror-polished cemented carbide was used. To form a coating film of the layer A using a target containing a metal component shown in Table 15, the layer A joseongjung, when forming the layer B ₄ C was used as B, C, Si, for each target of Cu.

At this time, the laminated film thickness (film thickness) was made constant at almost 3 micrometers (3000 nm) in each case. In addition, the thickness of layer A was 2-250 nm, and the thickness of layer B was each changed in the range of 0.2-30 nm.

In the sputtering film forming apparatus of FIG. 4, in the case of forming a metal film during film formation, in a pure Ar atmosphere, in the case of forming nitride, a mixed gas of Ar and nitrogen (mixing ratio 65:35), Ar in the case of carbonitride And a mixed gas of nitrogen and methane (mixing ratio 65: 30: 5) and a total pressure of 0.6 Pa were formed, and the thicknesses of the layers A and B were adjusted by the time for operating each evaporation source.

In the composite film forming apparatus of FIG. 5, a mixed gas of Ar and nitrogen (mixing ratio 50:50), a carbon dioxide mixed gas of Ar, nitrogen and methane (mixing ratio 50: 45: 5), and a total pressure of 2.66 Pa Was formed. In addition, layer A was formed at the arc evaporation source and layer B was formed at the sputtering evaporation source. In addition, the thickness of layer A and layer B was determined by the electric power ratio put into each evaporation source, and the laminated film thickness of the sum total of layer A + layer B was determined by the rotation period of a board | substrate.

About each of these formed films, the Vickers hardness of the film was evaluated by the micro-Vickers hardness tester (measurement load 25gf: Hv0.25).

In addition, the cross-sectional TEM photographs confirmed the lamination cycle and the thicknesses of the layers A and B. In addition, the composition was analyzed in depth direction of each film by Auger electron spectroscopy. These results are shown in Table 15.

As shown in Table 15, the comparative example of the numbers 1-6 is the case of the single | mono layer of only layer A which does not have layer B. FIG. On the contrary, in the comparison of compositions having the same layer A as Comparative Example 1, Inventive Examples 8 to 10, Comparative Example 3 and Inventive Examples 13 to 15, Comparative Example 4 and Inventive Examples 18 to 20, and the like, Compared with each comparative example, high hardness is ensured. Therefore, first, the effect of alternately laminating layers A and B in the present invention is supported.

Next, the example of numbers 7-16 has shown the effect of the film thickness of layer B. FIG. In the comparison within each group of Nos. 7 to 11 and 12 to 16 each provided with layer A and layer B of the same composition, Comparative Example 7, 12 is less than 0.5 nm in which the thickness of layer B is a lower limit. . In Comparative Examples 11 and 16, the thickness of the layer A is less than twice the thickness of the layer B. As a result, these comparative examples are given to Inventive Examples 8 to 10 and Inventive Examples 13 to 15, in which the relationship between the thicknesses of the layers A and B, and the thickness of the layers A and B satisfies the requirements of the present invention. The hardness is relatively low.

Next, the example of numbers 7-16 has shown the effect of the film thickness of layer B. FIG. In the comparison in each group of Nos. 7 to 11 and 12 to 16 each provided with layers A and B of the same composition, Comparative Examples 7, 12 are less than 0.5 nm in which the thickness of layer B is a lower limit. In Comparative Examples 11 and 16, the thickness of the layer A is less than twice the thickness of the layer B. As a result, these comparative examples are given to Inventive Examples 8 to 10 and Inventive Examples 13 to 15, in which the relationship between the thicknesses of the layers A and B, and the thickness of the layers A and B satisfies the requirements of the present invention. The hardness is relatively low.

Next, numbers 17 to 26 show the effect of the film thickness of layer A. In the comparison in each group of Nos. 17 to 21 and 22 to 26 where layers A and B of the same composition were provided, respectively, in Comparative Examples 17 and 22, the thickness of layer A was twice the thickness of layer B. Is less than. In Comparative Examples 21 and 26, the thickness of the layer A exceeded the upper limit of 200 nm. As a result, these comparative examples have hardness compared to the same group of Inventive Examples 18-20 and Inventive Examples 23-25 in which the relationship between the thickness of layer A and the thickness of layer A and layer B satisfies the present invention. Comparatively low

In addition, the invention examples 23-25 of layer A of Cr type component composition have a low hardness compared with invention examples 8-10, 13-15, 18-20 of Ti-type component composition, etc. However, as described above, when used for the sliding member, there is a characteristic that the attack to the counterpart material is lower than the Ti-based component composition.

Therefore, these results support the definition of the relationship between the composition and thickness of the layer A, the layer B, the thickness of the layer A and the layer B in the present invention, and furthermore, the meaning of the preferred regulation.

Example 4-2

Next, the layer A of various compositions was formed into a film, the film hardness was investigated, and the influence (effect) on the film hardness of the composition of the layer A in this invention was evaluated.

Under the same film formation conditions as in Example 4-1, a film having various compositions shown in Table 16 was formed. About the formed film, the film Vickers hardness similar to Example 4-1 was evaluated with the micro Vickers hardness tester (measurement load 25gf). In addition, the cross-sectional TEM photograph confirmed the lamination cycle and the thickness of the layers A and B. In addition, the composition was analyzed in depth direction of a film by Auger electron spectroscopy. These results are shown in Table 16 and Table 17 (continuation of Table 16).

As shown to Table 16, 17, the comparative example of the numbers 1-7 is the case of the single | mono layer of only layer A which does not have layer B. FIG. On the other hand, in Comparative Example 1, Inventive Example 11, Comparative Example 2, Inventive Example 18, Comparative Example 3, Inventive Example 14, Comparative Example 4, Inventive Example 23, and the like, the composition of the layer A was the same or in comparison with each other. Thus, each of these inventive examples ensures high hardness as compared with each comparative example. In addition, in the comparison of Comparative Examples 6 and 7 which made layer A TiN while comparing the same comparative examples, the comparative example 6 of the single layer only of the layer A which does not have layer B alternates between layer A and layer B alternately. It is lower in hardness than the laminated comparative example 7. Therefore, the results of these Table 16 also support the effect of alternately laminating layer A and layer B in the present invention.

In the present invention, the layer A is as described above, (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c )

[In the above, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and M is a metal selected from one or more of 4A, 5A, 6A, and Si. Element].

Here, in Table 16, the example of the same component system is compared. First, in the (TiAl) N system, Comparative Examples 9 and 13 in which the Al content is too low or too high out of the prescribed range of 0.4 ≦ x ≦ 0.8 are compared with Inventive Examples 10 to 12 in which the Al content is in the range. Low hardness

In (TiAlCr) N-based, Comparative Example 17 in which the Al content is too low out of the prescribed range of 0.4 ≦ x ≦ 0.8 may have a Cr content too high out of the prescribed range of 0 ≦ y ≦ 0.6, Hardness is low compared with invention examples 14-16 which content x is 0.45-0.65 and is in the said prescribed | regulated range of 0.4-0.8, and also in the more preferable specified range of 0.55-0.75.

Therefore, from these results, the meaning of the definition of Al content x of the layer A in this invention, or a more preferable definition is supported.

In the (TiAl) (BN) system, the content of B is too high out of the specified range of 0 ≦ a ≦ 0.15. In Comparative Example 26, the content of B is within the specified range of 0.15 or less, and more preferably 0.1 or less Hardness is low compared with invention examples 24 and 25 which are also within a prescribed range.

Therefore, from these results, the meaning of the definition of content a of B of the layer A in this invention, or a more preferable regulation is supported.

In the (TiAlCr) (CN) system, the content of C is too high out of the prescribed range of 0 ≦ b ≦ 0.3, and Comparative Example 29 has a content of C within 0.3 or less, more preferably within 0.1 or less Hardness is low compared with invention examples 27 and 28 which are also.

Therefore, from these results, the meaning of the definition of content b of C of the layer A in this invention, or a more preferable regulation is supported.

In the (TiAlV) (ON) system, Comparative Example 31 in which the O content is too high out of the prescribed range of 0 ≦ c ≦ 0.1 has a lower hardness than Inventive Example 30 in which the O content is within the specified range of 0.1 or less.

Therefore, these results support the significance of the definition of the O content of the layer A in the present invention.

Invention Examples 14 to 16 and 18 to 23 of Table 16 contain Cr, Si, Zr, Nb, Ta, and V as the additional elements M. Among these elements M, the hardness of the example containing Cr, Si, V, etc. was especially high. Therefore, the effect of improving the hardness of these elements M is supported. In addition, Examples 32 to 37 of the Cr-based component composition of the layer A have a lower hardness than the above-described invention examples of the Ti-based component composition. However, as described above, when used for the sliding member, there is a characteristic that the attack to the counterpart material is lower than the Ti-based component composition.

Example 4-3

Next, the layer B of various compositions was formed into a film, the film hardness was investigated, and the influence (effect) to the film hardness of the composition of the layer B in this invention was evaluated.

Under the same film forming conditions as in Example 4-1, films having various compositions shown in Table 17 were formed. About the formed film, the Vickers hardness of the film was evaluated similarly to Example 4-1 and 4-2. In addition, the cross-sectional TEM photograph confirmed the lamination cycle and the thickness of the layers A and B. In addition, the composition was analyzed in depth direction of a film by Auger electron spectroscopy. These results are shown in Table 18.

In addition, in the present Example, evaluation of the sliding motion characteristic of each film was evaluated by the ball-on-plate type reciprocating sliding motion wear friction tester. Evaluation conditions were performed by testing the counterpart material (ball) in a dry environment at a bearing steel (SUJ2, HRC60) having a diameter of 9.53 mm, room temperature, a sliding speed of 0.1 m / s, a load of 2 N, and a sliding distance of 250 m in a dry environment. Friction coefficient (mu) was evaluated.

In the present Example, the oxidation resistance of each film was evaluated from the oxidation start temperature. That is, the film sample formed about 3 micrometers in platinum foil was heated at the speed | rate of 4 degree-C / min in dry air from room temperature to 1100 degreeC using thermobalance, and the oxidation start temperature was determined from this oxidation weight increase curve. These results are also shown in Table 4.

As shown in Table 18, the comparative example of the numbers 1-7 is the case of the single | mono layer of only layer A which is not equipped with layer B. FIG. On the other hand, in comparison with Comparative Example 1, Inventive Examples 8 to 10 or Comparative Example 11, and Comparative Example 3 and Inventive Examples 12, 13, 15 to 17, and 19 to 21, each of these Inventive Examples was Compared with the comparative example, high hardness is secured. Therefore, the effect of laminating layers A and B in this invention alternately is also supported from the result of these Table 18.

In the present invention, layer B is a composition represented by the following formula (7) as described above.

Formula 7

M (B _a C _b N _1-abc O _c )

[In the above, M is a metal element selected from any one or more of W, Mo, V, Nb, a, b, c each represents an atomic ratio, 0≤ a≤ 0.15, 0≤ b≤ 0.3, 0≤ c≤0.1]

Here, in Table 18, the example in which layer B is the same component system is compared. First, in the W (CN) system, the content b of C is too high out of the prescribed range of 0 ≦ b ≦ 0.3, and the comparative example 11 has hardness and oxidation resistance in comparison with Examples 8 to 10 in which the content of C is within the specified range. Is low.

In the V (NO) system, Comparative Example 14, in which the content c of O is too high out of the specified range of 0 ≦ c ≦ 0.1, has a hardness and oxidation resistance in comparison with Examples 12 and 13, in which the content c of O is within the specified range. low.

In the Nb (BN) system, Comparative Example 18 in which the content a of B is too high out of the prescribed range of 0 ≦ a ≦ 0.15 is lower in hardness than the Inventive Examples 15 to 17 in which the content c of O is within the specified range.

Inventive examples 20 and (MoNb) (CN) of (MoNb) (CN) containing Mo of Nb (BN) -based invention examples 16 and 17 (comparative example 18 degrees) containing Nb as a composition of layer B Inventive Example 22 of the system and Inventive Example 21 of the (WAl) N system including W, the hardness of the coating was also high, but the oxidation resistance was particularly improved. Further, Example 19 of the (WV) N system has a high hardness of the film.

Inventive Examples 12, 13, and 26 containing V as the composition of the layer B (comparative example 14 degrees) in particular, had a low coefficient of friction.

Inventive examples 21, 22, 23, and 25 are 4A, 5A, 6A, and 1 of Si, which are different from those in the composition formula 3 of the layer B, except for W, Mo, V, and Nb. It is an example of invention in which the atomic ratio was substituted in the range of 0.3 or less with the metal element M1 chosen from more than a species. Inventive Example 21 replaces W with Al. Inventive Example 22 substitutes Mo for Si. Inventive Example 23 replaces V with Ti. As a result, the film hardness was increased.

In addition, Examples 24 to 28 of the Cr-based component composition of the layer A have a lower hardness than the above-described invention examples of the Ti-based component composition. However, as described above, when used for the sliding member, there is a characteristic that the aggressiveness to the counterpart material is lower than that of the Ti-based component composition.

Therefore, from these results, the meaning of each composition regulation of the layer B in this invention is supported.

As described above, the hard coating of the present invention and the method for controlling the crystal grain diameter of the hard coating can refine the crystal grain diameter of the rock salt-structure hard coating, thereby improving characteristics such as wear resistance of the hard coating. Therefore, it can be applied to wear-resistant coatings such as cutting tools based on cemented carbide, cermet or high speed tool steel, and sliding members for automobiles.

Moreover, according to this invention, the formation method of a hard laminated film and a hard laminated film excellent in abrasion resistance and oxidation resistance can be provided. Therefore, it can be applied to wear-resistant coatings such as cutting tools based on cemented carbide, cermet or high speed tool steel, and sliding members for automobiles.

Moreover, according to this invention, the composite film-forming apparatus and sputtering evaporation source which can obtain the hard film of a desired characteristic without the problem of film-forming forming can be provided.

Claims (23)

As a hard laminated film, the layer A and the layer B which consist of a specific composition are alternately laminated | stacked, the crystal structure of layer A differs from the crystal structure of layer B, and the thickness of layer A per layer is the thickness of layer B per layer The hard laminated film which is 2 times or more, the thickness of layer B per layer is 0.5 nm or more, and the thickness of layer A per layer is 200 nm or less. The method of claim 1, The said laminated layer A has a cubic rock salt structure, and said layer B has a crystal structure other than a cubic rock salt structure. The method of claim 2, The layer A is a compound of an element selected from at least one of 4A, 5A, 6A and Al and Si, and an element selected from at least one of B, C and N, The layer B is selected from compounds of an element selected from at least one of 4A, 5A, 16A and Al, and an element selected from at least one of B, C, N, or B, Si, Cu, Co, Ni The hard laminated film which is chosen from nitride, carbonitride, carbide of the element chosen from 1 or more types of C, or is selected from metal Cu, metal Co, and metal Ni. The method of claim 3, wherein The layer A is any one of nitride, carbonitride, carbide including any one of Ti, Cr, Al, and V, and the layer B is BN, BCN, SiN, SiC, SiCN, BC or Cu, CuN, CuCN, or Hard laminated film selected from metallic Cu. The method of claim 1, The hard laminated film which has the composition which the said layer A and the said layer B show below. Layer A: (Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e [In the above, X is one or two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si, and 0 ≦ α ≦ 0.9, 0 ≦ a ≦ 0.15, 0 ≤ b ≤ 0.3, 0 ≤ c ≤ 0.1, 0.2 ≤ e ≤ 1.1 (α represents an atomic ratio of X, and a, b, c represent atomic ratios of B, C, and O, respectively. to be] Layer B: B _1-st C _s N _t [In the above, 0 ≦ s ≦ 0.25, (1-s-t) /t≦1.5 (s and t each represent the atomic ratio of C and N. The same below) Or Si _1-xy C _x N _y [In the above, 0 ≦ x ≦ 0.25, 0.5 ≦ (1-x-y) /y≦1.4 (x and y represent atomic ratios of C and N, respectively. The same below)] Or C _1-u N _u [In the above, 0 ≦ u ≦ 0.6 (u represents an atomic ratio of N. The same below)] The method of claim 5, wherein A hard laminated film wherein α is zero. The method of claim 5, wherein A hard laminated film, wherein α is 0.05 or more. The method of claim 5, wherein The layer A has a rock salt cubic structure, and at least one of half widths of the diffraction lines from the (111) plane and the (200) plane observed in the X-ray diffraction pattern obtained by the θ-2θ method using CuKα rays is 0.3. Hard laminated film of more than °. The method of claim 1, The layer A is made of a composition of the following formula (1), wherein the layer B is a hard laminated film consisting of a composition selected from any one of the following formula (2), (3), (4), (5). Formula 1 (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ) [In the above, x, y, a, b, c each represent an atomic ratio, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, M is a metal element selected from at least one of 4A, 5A, 6A and Si] Formula 2 B _1-xy C _x N _y [In the above, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, B / N ≦ 1.51] Formula 3 Si _1-xy C _x N _y [Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.25, 0.5 ≦ Si / N ≦ 2.0] Formula 4 C _1-x N _x [Wherein, x represents an atomic ratio and 0 ≦ x ≦ 0.6] Formula 5 Cu _1-y (C _x N _1-x ) _y [Wherein, x and y each represent an atomic ratio, 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.5] The method of claim 9, The layer A is (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ), wherein x, y, a, b, and c each represent an atomic ratio, and 0.5 ≦ x ≦ 0.8 , 0.05 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and M is a metal element selected from one or more of Cr, V, and Si]. The method of claim 1, Layers A and B made of a specific composition are alternately stacked so that the compositions of layers A and B are different from each other, layer A consists of any one of the following formulas (1) and (6), and layer B has the following formula (7): Hard laminated film consisting of. Formula 1 (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ) [In the above, x, y, a, b, and c each represent an atomic ratio, 0.4 ≦ x ≦ 0.8, 0 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, and 0 ≦ c ≦ 0.1. , M is a metal element selected from at least one of 4A, 5A, 6A, and Si] Formula 6 (Cr _1-α X _α ) (B _a C _b N _1-abc O _c ) _e [In the above, α, a, b, c, and e represent atomic ratios, respectively, 0 ≦ α ≦ 0.9, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, 0.2 ≦ e ≦ 1.1 , X is a metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, Si] Formula 7 M _1-d M1 _d (B _a C _b N _1-abc O _c ) [In the above, M is a metal element selected from any one or more of W, Mo, V, Nb, M1 is selected from one or more of 4A, 5A, 6A, Si, excluding the W, Mo, V, Nb. The metal elements, a, b, c, and d, respectively, represent an atomic ratio, and 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, 0 ≦ c ≦ 0.1, and 0 ≦ d ≦ 0.3]. The method of claim 11, Hard laminated film in which said layer A is represented by (Ti _1-xy Al _x M _y ) (B _a C _b N _1-abc O _c ). [In the above, x, y, a, b, c each represents an atomic ratio, and 0.5 ≦ x ≦ 0.8, 0.05 ≦ y ≦ 0.6, 0 ≦ a ≦ 0.15, 0 ≦ b ≦ 0.3, and 0 ≦ c ≦ 0.1. , M is a metal element selected from one or more of Cr, V, Si] The method of claim 11, A hard laminated film having d = 0 in the layer B. The method of claim 11, The hard laminated film whose M in the said layer B is V. FIG. A method of forming a hard laminated film according to claim 1, comprising: a film forming atmosphere containing a reaction gas, using a film forming apparatus having at least one arc evaporation source and a sputtering evaporation source each having a magnetic field applying function, respectively, in the same vacuum vessel. In which the components of the layer A are respectively evaporated from the arc evaporation source and the components of the layer B from the sputtering evaporation source by simultaneously operating the arc evaporation source and the sputtering evaporation source, and the substrate is moved relative to each evaporation source, A method of forming a hard laminated film in which the layers A and B are alternately laminated. The method of claim 15, The said film-forming atmosphere is made into the mixed gas of the said reaction gas and the sputtering inert gas, and the partial pressure of this reaction gas is made into 0.5 Pa or more, The formation method of the hard laminated film. The method of claim 15, A method for forming a hard laminated film, wherein the arc evaporation source and the sputtering evaporation source are operated simultaneously to form a hard film containing nitrogen, wherein nitrogen is mixed in the sputtering gas and the partial pressure of the mixed nitrogen is 0.5 Pa or more. Deposition chambers; An arc evaporation source having a magnetic field application mechanism disposed in the deposition chamber; A sputtering evaporation source having a magnetic field applying mechanism, disposed in the deposition chamber; And Means for moving the substrate to be deposited between the arc evaporation source and the sputtering evaporation source, The film forming apparatus is characterized in that the magnetic field applying mechanism is configured such that magnetic lines of force between adjacent evaporation sources are connected to each other during film formation. The method of claim 18, During film formation, a sputtering gas is introduced from the vicinity of the sputtering evaporation source and a reaction gas is introduced from the vicinity of the arc evaporation source. The method of claim 18, The film-forming apparatus which uses the electrically insulating material in parts other than an erosion area | region as said sputtering evaporation source. The method of claim 18, A film forming apparatus, wherein, as the sputtering evaporation source, a shield is formed at a portion other than the erosion region to become a floating potential or a ground potential with respect to the potential of the sputtering target. A sputtering evaporation source used as a sputtering evaporation source for use in the film forming apparatus according to claim 18, wherein an electrically insulating material is used in portions other than the erosion region. A sputtering evaporation source used for the film forming apparatus according to claim 18, wherein a portion other than the erosion region is provided with a shield which becomes a floating potential or a ground potential with respect to the potential of the sputtering target.

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